Melekotu bitkisinin uçucu yağ ve kumarin bileşiklerinin incelenmesi

Ünal, Gonca
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Fen Bilimleri Enstitüsü
Yurdumuzda melekotu adıyla bilinen ve tek tür olarak bulunan Angelica Silvestris bitkisinin Belgrad Ormanından toplanan kök ve tohumlarının uçucu yag, ve kimyasal bileşenleri incelendi. Dünyada pek çok çeşidi bulanan orta ve kuzey Avrupa'da Uzak Doğu 'da yaygın olarak yetişen halk arasında ilaç, olarak sıkça kullanılan bitki ılıman, rutubetli yerlerde yayılış gösterir. Misk kokusuyla ünlü olan bitki kimyasal bileşenleri açısından da zengindir. Eter ile ekstrakte edilen öğütülmüş köklerden furokumarin bileşiği izole edildi. Eter ekstraktından preperatif ince tabaka kromotografisi ile önce kloroform, daha sonra kloroform: metanol (90:10) eluentleriyle izole edilen UVA'da şiddetli mavi fluoresans görülen maddenin yapı aydınlatılması için ^H-NMR-^C-NMR, Mass, UV- VTS, İR spektrumlarından yararlanıldı. Bileşik 2' [3'metoksi2'buten] psroralen olarak tanımlandı. önemli bir furokumarin olan ilaçlarda kullanılan ve umbel 1 if eronun Angelica Silvestris türündeki miktarı UV-VIS Spektroskopis ile tayin edildi. Ayrıca TLC, Kapiler Elektroforez Yöntemleriyle umbelliferon varlığı desteklendi. Çalışmalarda Standard olarak kullanılması için Pechmann Metodu ile umbelliferon sentezlendi. Umbelliferon Yüksek Floresans etkili bir madde olması ve toksik özellik içermemesi nedeniyle psoralen yerine vitiligo tedavisi için o/w emülsiyonu içinde kullanıldı. Psoralen UVA ile birlikte vitiligo tedavisinde kullanılan en etkin ancak çok toksik bir yöntemdir. Bu nedenle psoralen gibi yüksek floresans etkiye sahip bir kumarin olan umbelliferon bu amaçla hazırlanmış, uçucu yağlarla zenginleştirilmiş bir formulasyona eklenmiştir. Etki testleri denekler üzerinde bir dermatolog kontrolünde daha sonra yapılacaktır. Angelica Silvestris' in kök ve tohumunun su distilasyonu yöntemiyle uçucu yağı elde edilerek GC/MS analizi ile bileşenlere ayrıştırıldı. Kökteki uçucu yağın % 78' i, tohumdaki uçucu yağın ise % 95 'inin içerikleri belirlendi. Kökte %39 monoterpen % 6.8 seskiterpen, % 28 hidrokarbon, % 4 benzoid bulunurken, tohumda % 64.6 monoterpen, % 20 seskiterpen, % 5 hidrokarbon, % 0.122 benzoid ve % 0.137 di terpen bileşikleri vardır. Tohumda en yüksek orandaki bileşikler 6-terpinen (%21.845), 3-thujen ($12.232) p- simen (957.256), sabinen ($6.118) ; kökteki yüksek oranlı bileşikler Ö-pinen ($10.367), p-simen ($3.693), 6-terpinen ($ 3.307) dir. Tohumdan elde edilen uçucu yagm verimi köktekine göre çok yüksektir.
Angelica is an important member of the Umbellifereae family It is a special plant because of its misk scent. Angelica has also important medical effects and it is a valuable giant in the herb world. Therefore it is used widely as a folk medicine. Use has been made of leaves, stems, roots and seeds in medicine as well as in cooking. Angelica silvestris is one of the most important species of the Angelica. It resembles Angelica archangel ica as physiologically and contained the same chemical compounds. In Turkey, only the Angelica silvestris is grown. As it likes cool, and moistural climate, generally it is grown at rainy places and besides rivers. Believed to be originally a native of Syria, it has spread widely across the world, growing abundantly middle and north Europe and far East. On the other hand in our country it is found in Istanbul, Bursa, Sinop, Trabzon, Bolu, Zonguldak, Rize, Maras and Hatay districts. Angelica silvestris has 70-200 cm. long hollow stems and its basal leaves are ovate-elliptic, coarsely dentate, glabrous and 2-pinnate to ternate. It has umbels which are 15-90 rayed. Umbel laleous have 35-f lowers and they have pinkish-jwhite color. Its fruits are also glabrous and they have elliptic to orbicular shape. The special scent, richment in chemical compounds which cause important medical effects and the occurence of this plant as the only species in Turkey, are prompted us to study the essential oils and frocoumarin compounds of the Angelica silvestris Fresh roots and seeds of the Angelica silvestris were collected from Belgrad Forest, Yenice and Sinop districts. Both the roots and the seeds were cleaned and dried, and roots were also grinded. Grinded roots which have been collected from three different geographical regions were extracted with ether at room temperature. The ether extracts obtained were chromatographed on silica gel plates using chloroform as eluant. 6 different compounds were isolated from the ether extract by preperative thin layer chromatography. The third compound was rechromatographed by the same metod using chloroform: methanol (90:10) mixture. The compounds were coded as 1, 2, 3a, 3b, 4, 5, and 6 totally. Although the 1 and 3a compounds could be seen at visible region, all of the compounds except 3a could be observed both at 254 nm and at 366 nm. 3b compound was showed bright blue f lourescence absorption at 366 nm which has the brightest İX flourescence absorption among these seven compounds. Therefore this properties led us especially to characterize this flourescent compound. Based on 1H-NMR, ia!C-APT NMR, UV-VIS, IR, and Mass spectra the 3b compound was identified as 2' [3", Carboxy-2"butenyl] psoralen. Molecular weight of the compound was proved by m/z= 284 from the mass data. On the other hand [M-C0]*=256, (256-CH.-s)=241, (214-C0)=213 were the important fragments of the compound. Analyzing the 1H-NMR signal, the structure for the compound was obtained as "lineer furocoumarin" as shawn below. (2' [3" carboxy-2"butenyl ] psoralen) '.HNMR spectra showed that the presence of nonsubstitue pyron and benzene rings. The presence of -C£OH group was proved by the compound's IR and 1SC-NMR spectra (IR (max cnr1} 2500 (shoulder) and 1703, i:sC-NMR (ppm) :180 Umbel lif eron is a natural coumarin existing in Umbelliferous plants and it has antiarhytmic, antimutagenic, and anticoagulant effects and shows high flourescence absorption. These benefit properties of umbel 1 if eron forcet us to analyze the presence and if it is present the amount of the umbel lif eron in the Angelica silvestris. However IR. UV-VIS, capilary electrophoresis» and TLC methoda were used to indicate the presence and the amount of the umbelliferon. In order to use as a standard in the analysis, umbel 1 if eron was synthesized privately by Pechmann Method Because of the umbelliferon' s high flueorescent and nontoxic properties it may be tried in an oil in water (o/w) emülsiyon instead of psoralene which has a high toxic disadvantagous effect might used instead of psoralene because of its probable therapeuthic effect for vitiligo. Vitiligo is a disease of unknown orign which causes destruction of melanocytes in the skin, mucous membranes, the eyes, and occasionally in the hair bulbs and in the ears. The loss of melanocytes alters both structure and function of these organs. Vitiligo is a disease affecting about 1 % of the world's population. It affects equally individuals of all ethnic origins and both sexes. One fourth of patients note the onset of vitiligo before the age of 20 years, and 95 % before the age of 40. The first manifestations are loss of pigment (white spots), most commanly on the hands, feet, arms, face and lips, although vitiligo can begin on any part of the integument. The disease is usually progressive. Studies document that at least two thirds of patients with vitiligo significantly underachieve their potential owing to the psychosocial difficulties resulting rom the disfigurement. Depifmented skin is biologically altered by the loss of melanocytes. Depifmented skin has a markedly muted immune inflammatory response to a variety of noxious chemicals and other / inflammatory stimuti. The primary goal is to restore melanocytes to the skin so that the epidermis has a normal morphology. Such repigmented skin regains its normal immune / inflammatory functions -the second goal of treatment. Treatment for vitiligo is important to restore both the morphology and the function of the skin. As a secondary gain, patients also note improvement in their cosmetic appearance. Because melanocytes are indolent and slow responders to all current forms of therapy, therapy must be continued often for six months and sometimes for as long as twelve months for an optimal response. Vitiligo therapies can be classified as Non. surgical. Surgical and Adjunctive therapies. Surgical therapies are Dermabrasion, micropifmentation (Tattooing), Epidermal Graft, Autologous melanocyte Transplants. On te other hand Adjunctive Therapies are cosmetic camouflage, psychiatric counseling. Broad-spectrum sungcreens. Psoralen photochemotherapy is the most efficacious treatment currently axailable in the Nonsurgical Therapies for repifmentation of vitiliginous patches. But psoralen has many side effects including nausea and vomiting, proritus. photosensitivity, hypertrichosis, hyperpifmentation, xerosis, premature aging and skin cancers. Some data suggest that PUVA may involved in the formation of cataracts and in the alteration of cutaneous immunity. Because of these many side effects of the psoralen new Non- xi surgical treatments have been started to develope. Knell in and UVA, 1-phenyl alanine and UVA, melagenina are the some of these treatments in development. The high toxicity of the psoralene prompt us to use umbel 1 if eron incase of psoralene for he treatment of vitiligo with UVA. Since umbelliferon in like psoralene as a chemical character. The formulation of the oil in water (o/w) emulsion is göen below. The umbelliferon and UVA treatment will be tested on patients in a dermatoligical clinic. THE FORMULATION OF THE 0/W EMULSION OIL PHASE Mineral Oil % 12.6 Stearyl Alcohol & 4.1 Glicerylmonostearate % 2 Isopropylpalmitate % 3.2 Propyl paraben % 0.1 Essential oil of the Angelica sylvestris WATER PHASE De ionize water % 67.45 Cetyltrimethyl ammoniumchloride % 6.4 Glycerin % 4 Methylparaben % 0.1 Umbelliferon % 0.05 Angelica silvestris is a rich plant in chemical compounds with respevt to its essential oils and also its residual contents. The essentiol oil from the roots and the seeds of the herb was obtained by water distillation its chemical content was analyzed by using GC/MS spectrometer. The chemical content of the essential oils of the plant was composed of hydrocarbons, benzenoids, mono and, sesqui terpenoids. The highest percentage of these group in root and seed of the plant listed below.
Tez (Yüksek Lisans) -- İstanbul Teknik Üniversitesi, Fen Bilimleri Enstitüsü, 1996
Anahtar kelimeler
Kimya, Kumarinler, Melekotu, Essential oils, Chemistry, Kumarinler Melekotu, Essential oils