TAP CHi CONG THOONG
THANH PHAN HOA HOC CUA TINH DAU THONG Tl/ THONG MA VI
(P. MASSONIANA LAMB)
VUNG CHI LINH - HAI D I / O N G , VIET NAM
• HOANG TH! HOA - TANG THj PHUNG - TRAN TH! D!U
TOM TAT:
Bai vie't nghidn ciJu ve thanh phan hda hoc ciia tinh dau thdng ttf thdng Ma vi (p. Massoniana lamb) vung Cbl Linh - Hai Difdng, Viet Nam. Tinh dau thdng ma vi diTdc tach tif mu nhifa thdng theo phu'dng phap cho'ng cS't Idi cud'n hoi nifdc. Thanh phan cua tinh dau difdc xac dinh bang sac ky khi ghep khd'i phS (GC/MS) va detector Ion hda ngon lu'a gom 14 hdp chat sau: a-Pinene (85.98%), p-Pinene (4.43%), 3-Carene (2,47%), Longicyclene (1,88%), camphene (1,15%), Myrcene (0,94%), Limonene (0,91%), p-caryophyllene (0,38%), p-Phallenderene (0.37%), Tricyclene (0.23%), Verbenol (0,2%), Longipinene (0.14%), Longigyclene (0,11%).
Tuf khoa: Thdng Ma vi, tinh dau thdng, GC/MS.
I. Dalt vSn d6
Ho thdng (Pinaceace) la mdt ho ldn moc tu"
nhien va dtfdc trdng phd bie'n d nhieu ndi tren the gidi de thu cac san pham phuc vu cac muc dich khac nhau nhy go, nhifa, dnh dau... Tuy nhien, trong bcfn 100 loai thdng, chi mdt vai loai la nguon hieu quS de lay nhifa (resin) thu linh dau nhu' P.
ellioltii Engelm, P. massoniana v^ P. kesiya Royale ex Gordon, P pinaster. Alton (Portugal), P.
merkusii Jungh. va Vriese,... Cac loai thdng khac nhau, difdc trong d cac viing dia iy khac nhau se cho linh dau cd ham lifdng va cha't lu'dng khac nhau [2].
Tinh diu thdng (Turpentine) la mdt bdn hdp nbilu hdp cha^t pbiJc tap chu yeu la cac hdp chat terpenoid nhu": sesqulterpenoid va monoterpenoid difdc sii dung trong nhieu ITnh vifc ky thual cung nhu' cac muc tieu y difdc hoc. Loai hdp cha'l va thanh phan khd'i lifdng cua mdi loai phu thudc vao
loai thdng, dilu kien dia ly ctia vilng trong cay. Vi du, theo nghien ciJu cua Gscheidmeier va Fleig (1996), va sau dd la cua (2002), thanh phan chinh cua tinh dau thdng difdc san xua't tai Hy Lap la a- pinene (92 - 97%), p -pinene (1 - 3%). Trong khi dd, tinb dau thdng d An Dd cd ham lu'dng tifdng dd'i tha'p a-pinene (20-40%) va p - pinene chiem ham lu'dng lii (5-20%) [3]. Tai Vidt Nam, theo nghien cu'u cua Nguyen Van DSu va Phan Td'ng Sdn thdng ba la tai Lam Dong cd ID hdp chat cd ban, trong dd pinene (62,6%), p -pinene (4%), p - Phellandren (26,4%) va mdt so' hdp cha't khac [4].
Sac ky khi ghep kho'i phd' (GC-MS) la mot cdng cu hieu qua va chinh xac de dinh tinh cung nhu' dmh lu'dng cac thanh phan cua dnh dau. Dd chinh la cdng cu chuan de xac dinh cha't li/dng va gia tri cua dnh dau [6].
O Viet Nam, thdng Ma vT da difdc trong tai Lang Sdn, Quang Ninh, Ha Giang.,. Tai Chi Linh, 3 9 4 So 6 - T h d n g 4/2019
HOA HOC-CONG NGHE THlfe PHAM
Hal Dtfdng, thdng Ma vl cd dien tich tifdng ddi Idn tai hai khu di tich la Cdn Sdn va vung doi Phu'dng Hoang, ndi cd den thd nha giao Chu Van An la nguon IS'y nbi/a doi dao phuc vu cho nganh cdng nghiep thu tinh dau. Trong nghien cu'u nay, tinh d^u thdng Ma vi (P. massoniana Lamb) du'cfc tach tiJ mu nbifa thdng thu tai doi thdng Cdn Sdn - Chi Linh, Hai Du'dng theo phu'dng phap chifng cat Idi cud'n hdi mfdc. Thanh phan cua tinh dau difdc xac dinh bang sic ky kbi ghep khd'i pho (GC/MS). Cac thdng so'khac cua tinh dau du'dc xac dinh la: Ty khd'i d 20"C, Chi sd'kbuc xa d 250c, Gidi han sdi.
2. Nguyen lieu va phifdng phap nghien cii'u 2.1. Nguyen lieu nghien cdu
- Mii nbifa thdng du'dc trich iriJc tiep tii cay thdng Ma vl (P. massoniana Lamb) viing doi thdng Con Sdn - Chi Linh - Hai Difdng.
2.2. PhUdng phap nghien ciiu
- Phu'dng phap chifng cat tinh dau thdng: 350g mfi nhtfa thdng Ma vi difdc cho'ng ca't Idi cud'n hdi nUdc cho dd'n khi phan nu'dc ca't sang trd nen trong suol (2,5h). Phan dau difdc tach rieng bang pbeu chie't. Lam khan phan dau bang natri sunfat. Tinh dau difdc bao quan trong tu lanh trifdc khi dem di phSn tich bang GC-MS.
- Hieu sua't thu tinb dau difdc tinh nhif sau:
H = ni2 xl00%
Trong dd: mj (g): Khdi lu'dng dnh dau thu difdc sau chifng cat, m2 (g): Khdi kfdng mu nhifa mang di chUng cS't.
2.3. PhUdng phap phdn tich
- Thanh phan dnh dau du'dc phan tich bang sac ky khi ghep khd'i phd GC/MS vdi deciecior ion hda tren may Agilent 6890N, Hoa Ky, tai Vien Hda hpc cac hdp cha't Thien nhien, Vien Han lam Khoa hoc va Cdng nghe Viet Nam. Dilu kien chay mau: cot HP-5 (25 m /0.25 mm, chieu day cdt 0.11 pm), su" dung khi mang HeHum vdi td'c do ddng 0.8 mL/pbut, the tich mau 0.5 pi vdi ti le chia ddng 1:50. Nhiet do do mSu tu- SCC (0.5 min) tdi 250"C, vdi td'c dp nang nhiet 4*'C/phut.
Khd'i phd Agilent 5975B vdi nguon ion hda 70 eV, 230»C.
- Ty khd'i d 20°C, Cbi sd khuc xa d 25''C, Gidi han sdi "C, Chi sd axil du'dc xac dinh theo TCVN 189-66
3. Ke't qua va thao lu^n
3.1. Hieu sita't thu tinh dau thong tii nhiia So vdi thdng nhifa va thdng ba la thi thdng Ma vT cho nang suS't nhifa th^'p hdn. Song vin la ngudn cung ca'p nhifa de la'y colophan va linh dau thdng dangke [6].
Dd'i vdi thong Ma vT trdng tai vilng Cdn Sdn Chi Linh, Hai Difdng, theo ke't qua chimg cat, tinh dau thdng thu difdc tif nhifa dat hieu suat 24%. Tha'p hdn so vdi ihd'ng ke trung binh tren. Tuy nhien, ham lifdng linh diu tren cung da tifdng dd'i hieu qua bdi bdn canh dd cdn thu colophan phuc vu ky thuat.
3.2. Cdc chi tieu ky thu4t cua tinh ddu thong Cac cbl tieu ky thuat cua tinh dau thdng dUdc xac dinh theo TCVN 189-66. Ke't qua thu du'dc nhtf sau:
Bdng 1. Cht tieu ky thugt cua tinh dau thong Ten
chi tieu Ty khdi d
20"C Chi sd khuc
xa d 251'C Gia tr[ xac d[nh dUdc 0,86
1,4630 Ten chi tieu Gidi han sdi
°C Chi so axit
Gia ir\ xac dinh dtfdc 156
0,6
Vdi ke'l qua nay, cd the tha'y dnh dau thdng cua ihdng Ma vl trdng lai Chi Linh, Hai Difdng da dat lieu chuan ky thuat theo TCVN 189-66.
3.3. Thanh phdn hda hoc ciia tinh ddu thong xdc dinh bang GC/MS
Ke'l qua phan tich GC/MS vdi decteclor ion hda ngon liJa difdc irinh bay trong Bang 2.
Theo ke't qua nay, lijf tinh dau thdng chifng ca't ttf nhtfa thu du'dc 14 hdp cha't. Thanh phan nhieu nhat la cac Monolerpene vdi 9 hdp chat trong dd pinene (bao gdm a-pinene va P-pinene) chiem tdi 90,41% va cd mdt alcohol vdi vdng monolerpene.
Nhdm cha't thiJ 2 thu difdc la cac sesquiterpene vdi 4 hdp chat.
3.3.1. Nhdm monolerpene
Nhdm monolerpene xac dinh du'dc gdm cac hdp cha'l CO ca'u true dtfdc trinh bay trong Hinh 1.
Tdng ham lu'dng cac monolerpene chiem idi 96,59% cac hdp cha'l cd trong dnh dau thdng. So vdi cac loai thdng khac, ham lu'dng pinen irong linh dau tinh dau Ihong Ma VI (P. massoniana Lamb) lai Chi So6-Thang 4/2019 395
TAPCHiCQNeTHU0NG
Bang 2. Thdnh phdn hoa hoc cue tinh ddu thong xac dmh bdng GC/MS
TT 1 2 3 4 5 6 7
Hdp chat Tricyclene a-Pinene Camphene
Sabinene p-Pinene Myrcene 3-Carene
Thdi gian ItJu (phut)
9 08 10.17 10 63 11.33 11.50 1174 12 54
Ham iiiong % 0.23%
85 98%
1,15%
0,11%
4 43%
0,94%
2,47%
TT 8 9 10 11 12 13 14
IHdp chat Limonene p-Phallenderene
Verbenol Longipinene Longicyclene Longifolene fS-caryophyilene
Thdi gian iiiu (phut) 13.15 13.22 17 29 24.56 25.31 26.48 26.83
Ham luong % 0,91%
0.37%
0,2%
0.14%
0,11%
1,88%
0,38%
Hinh 1: Ca'u true cua cac Monoterpene co trong tinh ddu thong chief xuat tij thong vung Chi Linh - Hai Diidng
HaC HjC-
OH3 a-Pinene
H
^ : ;
p-Pinene H3C
HaC-
H3C CH3
Myrcene P-Phallendercne
H
3-Carene Limonene Camphene Tiicyclene Tram-Verbenol
Linh, Hai Du'dng kha cao, len tdi 90,41% cao hdn so vdi thdng ba la (P. Kaysia Royle) dtfdc trdng tai Lam Dong, Viel Nam cd ham lu'dng monoterpene la 71,1%. Trong thanh phan con cd mdt monolerpenol la Trans-Verbenol (ham kfdng 0,2%) cd vai tro nhU mdt chat dan du cdn trijng tdi cay. Verbenol nay ciing du'dc tim tha'y trong Finns sylvetris L. vdi ham lu'dng 1.53%. So vdi thdng Ma vT tai mien Nam Trung Qud'c - vung nguyen san ciia thdng Ma vT, chi cd 7 monoterpene difdc xac dinh la alpha-pinene (chiem 85%) sau dd la bela-pinene, limonene Myrcene, 3-Carene, Camphene, Tricyclene, Bomeol [7].
Cac hdp chat khdng cd trong thdng Ma vT tai Trung Qud'c la p-Phallenderene, Sabinene va Trans-Verbenol Nhu' vay, hoat cha'l chinh la alpha-pinene lu'dng dd'i gidng nhau trong gid'ng nay
du'dc trdng d ca Trung Qud'c va Viet Nam, nhifng so' lu'dng va bam lifdng cua cac hdp chat khac cd thay ddi tuy thudc vao viing mien, cd nhifng hdp chat khdng cd tai thdng Ma vi Trung Qud'c lai xuS't hien irong tinh ddu thdng Ma vT du'dc trdng lai Chi Linh. Hai Difdng.
So vdi thdng Pmus sylvestris L. from liJ Denizli, Thd Nhi Ky cd ham lu'dng a-pinene cao nha't la 43,60%. Cac monolerpene khac la 3-carene va bmonene cung dUdc tim tha'y trong gid'ng thdng nay vdi ham lifdng lan lu'dt la 29,40%, 9,68% cao hdn nhieu lan so vdi thdng Ma vltai Chi Linh, Hai Difdng cd ham lu'dng la 2,47% va 0,91% [8].
Thdng Pinus roxburghaii difdc trdng tai Pakistan cd 12 monoterpene chiem 67,9% vdi ham lu'dng cac hdp cha't lan lu'dt nbif sau: pinene (41.9%), camphene (0.9%), 3-carene (16.3%), o-cymene 396 So 6-Thang 4/2019
HOA HOC-CONG NGHETHtfC PHAM
(0.4%), limonene (L7%), phellandrene (0.7%), terpinene (0.2%), p-cymene (1.9%), terpinenol (1.8%), lerpinyle acetate (0.8%), l-terpinen-4-ol (0.2%), borneol acetate (1.1%). Cd the tha'y, tuy so lifdng monoterpene nhieu hdn, nhtmgtdng ham lifdng cac cha'l trong loai thdng nay lai thap hdn so vdi P. massoniana Lamb du'dc trdng tai ca Trung Qud'c va Viet Nam [3].
3.3.2. Cdc hop cha't sesquiterpene Cac hdp cha'l sesquiterpene xac dinh difdc trong tinh dau thdng difdc trinh bay trong Hinh 2.
tinh dau ihdng lif Pinus roxburghaii Irdng tai Pakistan, cac Sesquiterpene xac dinh difdc la:
caryophyllene (12.3%), farnesene (0.6%), caryophyllene oxide (1.0%), Famesy! acetate (0,2%), Bulanoic acid,3-methyl-,2- phenylethylester (0,3%) [3]. Tong ham lu'dng Sesquiterpene itfdng doi cao so vdi Ihong Ma vi.
Nhif vay, cd the tha'y do dac thii ve dieu kien Ihd nhUdng ma thdng Ma vT trdng lai Chi Linh, Hai Du'dng cd sd lifdng Sesquiteipene il hdn d cac viang khac, ham lu'dng cung tha'p hdn.
Hinh 2: Ca'u true CIJO cac Sesquiterpene co trong tinh dau thong chief xuat /u" thong vung Chi Linh - Hai Di/dng
CH3 "^c ^ „ . H3C CHa
a-Longi pinene Longicyclene Bdn hdp chat Sesquiterpene nay ciing du'dc lim
thay trong thdng Ma vT trong lai mien Nam Trung Qud'c vdi ham lu'dng lu'dng dd'i gan nhau. Tuy nhien, cd 7 Sesquiterpene dtfdc tim tha'y trong thdng trdng tai Trung Qud'c la: Ylangene, Copaene, Sativene, Humulene, p - Farnesene, Germacrene - D, 5 - Cadinene [7j. Trong tinh dau Pinus sylvetris L., ham lu'dng cac Sesquiterpene a-longifolene la 9.59% , p-caryophyilene (1,65%), a-longipinene (0,71%), longicyclene (0,66%) cao bdn nhidu so vdi Sesquiterpene trong tinh dau thdng (P. massoniana Lamb) tai Chi Linh, Hai Du'dng vdi cac gia tri lu'dng lfng la: 1,88%, 0,38%, 0,14% va 0,11% [8]. Trong
4. K^t luSn
Tif nhifa thdng Ma vT P. massoniana Lamb du'dc trdng lai Cbi Linh, Hai Difdng bang phu'dng phap chifng cat Idi cud'n hdi nu'dc thu du'dc tinh dau thdng vdi hieu sua't 24%. Tinh dau cd cac cbi tieu ky thuat thda man TCVN 189-66. Thanh phan hda hpc xac dinh theo GC/MS cho tha'y tinh dau thdng cd chiJa 9 hdp chat monoterpene (a-Pinene, p-Pinene, Myrcene, 3-Carene, Limonene, Camphene, p-Phallenderene, Tricyclene, Sabinene, Trans-Verbenol) va 4 hdp cha't sesquiterpene (p-Caryophyllene, a-Longipinene, Longicyclene, Longifolene) •
TAI LIEU THAM KHAO:
!. T. Teshome (2011), Analysis of resin and turpentine oil constituents of Pinus paluki giown in Ethiopia.
Agriculture and Forestry Ee-JRIF Vol 3, pp (38 - 48).
2. Nguyen Hoang Sa (2017), Nghien citu thdnh phdn hda hpc vd hoat tinh sinh hpc ciia cdc loai Id kim: Pmus Dalatensis, Pinus Kesiya vd Podocarpus Neriifolius d Viet Nam. Luan dn tien si Hda hoc, Hoc vien Khoa hoc vd Cong nghS, Vien Hdn lam Khoa hoc Viet Nam.
So 6 - T h a n g 4/2019 397
TAPCUiCONCTHmG
3. Aminara Hassan, imran Anijidl (2009), Cas chromatography-mass spectrometric studies of essential oil of Pinus roxburghaii steins and their antibacterial and antifungal activities. Journal of Medicinal Plants Research, Vol. 3(9). pp. 670-673.
4. Phan Tdng Son, Nguyhi Vdn Ddu (1987), Ve thdnh phdn hoa hoc ciia thong ba Id (Pinus Kaysia Royle) viing Lam Dong, Viet Nam, Tap chi Khoa hpc, 37-4!.
5. Lanhua Guan, Suhaiyanto, and Susumu Shiraishi (2011), Isolation and characterization of tetranucleatide microsatellite loci in Pinus massoniana (pinaceae), American Journal of Botany, Volume !0 216-217.
6. Su Feng, Weicai Zeng, Fan Luo, Jian Zhao, Zhirong Yang, Qun Sun (2010), Antibacterial activity of organic acids in aqueous extracts from pine needles (Pmus massoniana Lamb, Food Science and Biotechnology, Volume 19 (I), pp 35-41.
7. Liu Q, Zhou Z, Wei Y, Shen D, Feng Z, Hong S (2015) Genome-Wide Identification of Differentially Expressed Genes Associated with the High Yielding of Oleoresin in Secondaiy Xylem of Masson Pine (Pinus massoniana Lamb) hy Transcriptomic Analysis. PLoS ONE 10(7): e0132624 https://doi.org/I0.1371/journal.pone.0132624]
S. Uhrahim Ttfmenl, Markku Reunanen (2010), A Comparative Study on Turpentine Oils of Oleoresins of Pinus sylvestris L. from Three Districts of Denizli, Rec. Nat. Prod. 4:4, 224-229.
Ngay nhan bai: 23/3/2019
Ngay phan bi^n danh gia va siJa chffa: 31/3/2019 Ngay cha'p nh§n dang bai: 11/4/2019
Thong tin tdc gid:
HOANG THI HOA - TANG THI PHUNG - TRAN THI DIU Trifdng Dai hoc Sao Do
CHEMICAL COMPONENTS OF ESSENTIAL OIL OF P. MASSONIANA LAMB PLANTION IN CHI LINH - HAI DUONG, VIETNAM
• HOANG THI HOA
• TANG THI PHUNG
• TRAN THI DIU Sao Do University ABSTRACT:
This study is to analyze chemical composition of essential oils from p. Massoniana lamb pine m Chi Linh region, Hai Duong Province, Vietnam. Essential oil of P. massoniana Lamb was separated from resin by hydrodistillation. Turpentine oil was analyzed by GC/MS. Fourteen components were identified in the oil. Major components m turpentine oil were a-pinene (85.98%), p-pinene (4.43%), 3-Carene (2,47%), Longicyclene (1,88%), Camphene (1,15%), Myrcene (0,94%), Limonene (0,91%), P-caryophyllene (0,38%), p-Phallenderene (0.37%), Tricyclene (0.23%), Verbenol (0,2%), Longipinene (0.14%) and Longigyclene (0,11 %).
Keywords: P. massoniana Lamb, Turpentine oil, GC/MS.
3 9 8 So 6 - T h d n g 4/2019
