Chemistry of Natural Products

SEMESTER FINAL EXAM MATERIALS CHEMISTRY CULTURE

Name                          : Yunita Rubi Lestari

NIM                            : RSA1C110007

Course                        : Chemistry of Natural Product

Credits                        : 2

Lecturer                     : Dr. Syamsurizal, M.Si

Time                           : 22-29 December 2012

 

1). Jelaskan dalam jalur biosintesis triterpenoid, identifikasilah faktor-faktor penting yang sangat menentukan dihasilkannya triterpenoid dalam kuantitas yang banyak.

Answer :

Triterpenoid
Triterpenoid carbon skeleton is a compound derived from the six units (units) and in the biosynthesis of isoprene derived from C30 acyclic hydrocarbons, ie skualena.
More than 4000 kinds of triterpenoids have been isolated with more than 40 kinds of basic framework that has been known and in principle is the cyclization of skualen. This compound is a compound colorless, crystalline, often high melting point and active optics.

Triterpenoids consisting of frame with 3 cyclic 6 which joined berupaka cyclic 5 or 6, which has a cyclic 4 functional groups on specific cyclic. While naming further simplified by giving the numbering on each carbon atom, thus facilitating the determination of the substituents on each carbon atom. Terpenoida a wide range of structures that arise as a result of subsequent secondary reactions such as hydrolysis, isomerization, oxidation, reduction and cyclization over-geranil, farnesil-and-geranil geranil pyrophosphate.

Triterpenoid widespread in resin, cork and kutin plants. Resin is a triterpenoid acid often together with xanthan gum polysaccharide in amber. Triterpenoid alcohol also are free and as glycosides. Triterpenoid acyclic hydrocarbons skualena important only for the first time isolated from shark liver oil but is also found in some nights epikutikula and vegetable oil (olive oil). Triterpenoid compound best known as lanosterol contained in wool grease, yeast and some compounds of higher plants. Triterpenoid eufol tetrasiklik like alcohol and acids from Euphorbia sp of Elemi Canarium commune.

Triterpenoids are pentacyclic triterpenoid most important thing. These compounds are found
in seprimitif sphagnum plants but the most common is the seed plants, free and glycosides. Triterpenoid nonglikosida often found as excretion and the work as a protective cuticle or cause resistance to water.
Several kinds of physiological activity of triterpenoids which is the active component of the plant has been used as a medicinal plant remedy diabetes, menstrual disorders, pecks snake, skin disorders, liver damage, and malaria.
Skualena is a steroid derivative of the basic framework has four rings as follows:


Triterpenoids have a very bitter taste, especially present in Rutaceae plants, Meliceae and Simaroubeaceae as limonin in citrus fruits (also classified as a sense of bitter alkaloids) and kukurbitasin D in Cucurbitaceae plants and diosgonin. In the form of triterpenoids found in plant sap of Euphorbia and Havea.

Triterpenoid Biosynthetic

Based on its mechanism of acetyl-CoA via the mevalonic acid pathway produces isopentyl pyrophosphate (IPP), which later became dimethyl berisomerisasi alipirofosfat (DMPP) assisted with the isomerase enzyme, which produces IPP and DMPP join geranil Pyrophosphate (GPP) to form monoterpenoid compounds, then GPP and IPP merged by the same mechanism produces farnesil pyrophosphate (FPP) to form sesquiterpenoid compound, combined with the subsequent FPP FPP with a path similar mechanisms will produce triterpenoid compounds. In this biosynthetic pathway could be modified to increase the amount of production triterpenoid more and with less time.
One of the factors that determine the quantity produced triterpenoid much on triterpenoid biosynthetic pathway enzymes. The enzyme in the biosynthesis of triterpenoids may also determine the amount that will be generated. This is because the growing number of enzymes that act on biosynthetic pathways, it will be the more triterpenoid obtained. The use of enzymes in the biosynthesis of the triterpenoids itself as a catalyst. Where it is known that the function of the use of enzymes that can accelerate the reaction, but did not participate react. But in this biosynthetic pathway inhibition also occurred that would lead to mevalonic triterpenoids produced a little.

2). Jelaskan dalam penentuan struktur flavonoid, kekhasan signal dan intensitas serapan dengan menggunakan spektrum IR dan NMR. Berikan dengan contoh sekurang-kurangnya dua struktur yang berbeda.

Answer :

Flavonoids are a group of phenolic compounds found in fruits and vegetables. Compound has 15 carbon atoms, consists of two substituted benzene rings connected by a single aliphatic chain containing three carbon atoms (Figure 1.7). The basic framework of the system structure of flavonoids is C6-C3-C6.

 

Figure 1.7. structure of Flavonoids

Flavonoids have been studied have a wide range of biological activity. Flavonoids act as anticancer, antiviral, anti-inflammatory, reducing the risk of cardiovascular disease and play a role in the capture of free radicals. The power of the antioxidant activity of flavonoids depends on the number and position of OH groups contained in the molecule. The more substitutes a hydroxy group on the flavonoid, the greater the activity antiradikalnya. The existence of ortho-catechol group (3'4'-OH) on the B ring of flavonoids is an important determinant of high antioxidant capacity (Andersen et al., 2006).

• The intensity of the IR absorption:

In the long-wave infrared spectrophotometry and wave number is the value used to indicate the position of the absorption spectrum.
Where in the intensity of the absorption of flavonoids is displayed hydroxyl (3227 cm-1) and (1628 cm-1).

• The intensity of the NMR absorption spectrum:

Samples under appropriate conditions flavonoids can adsorbing area radio frequency electromagnetic radiation, radio depends on the nature of the sample. A plot of peak frequency versus absorption peak intensity gives an NMR spectrum

3). Dalam isolasi alkaloid, pada tahap awal dibutuhkan kondisi asam atau basa. Jelaskan dasar penggunaan reagen tersebut, dan berikan contohnya sekurang-kurangnya tiga macam alkaloid.

Alkaloid is an alkaline compound containing nitrogen atoms satuatau more and usually a cyclical system. Alkaloids mengandungatom carbon, hydrogen, nitrogen, and usually contains many alkaloids oksigen.Senyawa contained in the roots, seeds, wood and leaves daritumbuhan and also of animals. Metabolismedari alkaloid compounds is the result of plant and used as a backup for the synthesis of the plant alkaloid protein.Kegunaan is as protective of pests, plants and regulator amplifier hormones work. Alkaloids have physiological effects. Source is a flowering plant alkaloid, angiosperms, animals, insects, marine organisms and microorganisms. Mengandungalkaloid plant families that are Liliaceae, solanaceae, Rubiaceae, and papaveraceae (Tobing, 1989).

Classification of Alkaloids

Alkaloids not have a systematic name, so namadinyatakan as trivial as codeine, morphine, heroin, quinine, kofein, nicotine. Almost all were given the trivial name suffix-in that characterizes alkaloid.Sistem alkaloid widely accepted classification is the division alkaloidmenjadi three groups, namely real alkaloid, protoalkaloid and pseudoalkaloid.Suatu ways of classifying alkaloid is a nitrogen based heterocyclic jeniscincin which is part of the structure molekul.Jenisnya namely pyrrolidine, piperidine, quinoline, isokuinolin, indole, pyridine dansebagainya (Robinson, 1995). The structure of the types of alkaloids presented dalamgambar
 

Isolation of Alkaloids

a.       Alkaloid extracted from the leaves of plants, flowers, fruit, bark, dried and crushed danakar. Extraction of alkaloids in umumadalah as follows:
Alkaloid extracted with certain solvents, such as ethanol, and then evaporated.

b.       Ekstrak obtained given inorganic acids to produce a quaternary garamamonium then extracted again quaternary ammonium

c.       Garam obtained reacted with natriumkarbonat to produce these alkaloids kemudiandiekstraksi free with certain solvents such as ether and chloroform.

d.       Campuran - a mixture of alkaloids obtained finally separated in various ways, such as chromatographic methods (Tobing, 1989).

There are other ways to get the alkaloids from the acid solution by absorption using Lloyd reagent, and then eluted with basaencer alkaloids. Alkaloid that is hydrophobic absorbed by XAD-2 resin and dielusidengan acid or ethanol-water mixture. Many alkaloids which can be precipitated by Mayer's reagent (potassium mercury (II) iodide) or salt Reineccke. This study used a general way that the isolation of alkaloids extracted with an organic solvent, acidification, formation of quaternary garamamonium with a base, extraction with organic solvents, and purification using column chromatography, thin layer chromatography, ataupuninstrumen-electronic instruments (IR, GC-MS, UV -Vis)

4). Jelaskan keterkaitan diantara biosintesis, metode isolasi dan penentuan struktur senyawa bahan alam . Berikan contohnya.

Answer :

Biosynthesis (also called biogenesis or "anabolism") is an enzyme-catalyzed process in cells of living organisms in which a substrate is converted to more complex products. Biosynthesis process often consists of several enzymatic steps in which the product of one step is used as substrate in the following step. An example for such a multi-step biosynthetic pathways are those for the production of amino acids, fatty acids, and natural products. Biosynthesis plays a major role in all cells, and more specifically the metabolic routes combined constitute general metabolism. Six organelles within cells that is involved in biosynthesis. Ribosomes, chloroplasts, smooth endoplasmic reticulum, rough endoplasmic reticulum, plastids, and Golgi bodies

Basically isolation of chemical compounds from natural ingredients it is a business how to separate the compounds were mixed so that we can produce a pure single senayawa. Let's take just one example, how to isolate compounds from plants. Plants that contain thousands of compounds, both of which are categorized as primary metabolites or secondary metabolites. Usually the isolation of compounds from natural ingredients ni hopes to isolate secondary metabolites, secondary metabolites due believed and has been shown to provide benefits for human life. Antaralain benefits are in the areas of agriculture, health, food, cosmetics etc.

NMR (Nuclear Magnetic Resonance) spectroscopy is a method that is very important in determining the structure of organic compounds. We know that all organic compounds metabolite natural products and bioactive both lacked the NMR, both 1H-and 13C-NMR were expressed by a number of resonance peaks and prices dimiliki.setiap NMR chemical shifts of carbon atoms in the molecule has a peak or a shift NMR chemical which depends on the position of the carbon atoms in the structure of the molecule. The position of the carbon atom gives specific conditions that lead to each carbon atom in an organic molecule has a peak or specific NMR chemical shifts as well. Trait that would distinguish one molecule with another molecule. The number of peaks and NMR price is used as the basis for the determination of a molecule.

Biosynthesis, isolation and structure determination methods that are important to know and mempelajasi compounds of natural ingredients. The third method is highly related to one another. In the process of biosynthesis of us can know the process of formation of compounds of natural ingredients that only lasted in living things. Where in this process we mangetahui that there are certain enzymes that are involved. In the biosynthesis of these different types of reactions occur to produce a compound. By studying the biosynthesis of these compounds produced as well, then we can know the properties of these compounds are natural materials, so we can design an isolation method based on the nature and reactions of these compounds. For example, we can choose a suitable solvent and other treatments to obtain pure substances. Once isolated, then the knowledge-knowledge that has been known in advance, we can carry out the procedure of determining the structure of the compound, for example by spektoskopi NMR, IR and UV.

 

CHOLESTEROL

Cholesterol is a complex molecule, a part of the family of organic molecules called sterols. It was discovered by Michel Chevreul in 1812, and has been studied by many researchers since then. Thirteen scientists have received Nobel Prizes studied, including Adolf Windaus.

Cholesterol is a very important part of cell membranes. The membrane is required to keep our cells intact, and to regulate the flow of nutrients to and fro inside and outside the cell. More cholesterol in the membrane, which is rigid. Neural networks in the brain and spinal marrow, which requires a lot of isolation cells, rich in cholesterol.

Cholesterol is made by the liver. Mostly used to make bile. Bile is a complex mixture including cholic acid, amino acid and desoxycholic cholanic. These acids are stored in the gall bladder, and released into the intestine during the digestive process. Bile emulsifies fats that we eat, so that the digestive enzymes to break them.

Cholesterol is also used to make hormones that are essential for normal body function. These include corticosteroids, which are essential for fighting infections and allergies. Cholesterol is an important precursor molecules for the synthesis of vitamin D and steroid hormones, including the adrenal gland hormones cortisol and aldosterone, as well as the sex hormones progesterone, estrogen, and testosterone, and derivatives.

So why do people talk about good and bad cholesterol?
Cholesterol is used to make bile and also to make hormones that are essential for normal body function.

Some of cholesterol made by the liver is secreted into the blood to be transported to other tissues. In the blood, it is associated with another chemical called lipoproteins. If there is a lot less lipoprotein and cholesterol, known as high-density lipoprotein (HDL). HDL is used by the body to make other types of molecules, and what is known as good cholesterol.

If the opposite is true, this is known as low density lipoprotein (LDL). LDL is not easily transported in the blood, and will be deposited in the arterial wall. These deposits are called plaques. If there is too much LDL plaque or if they are close to the heart, it can cause a stroke or heart attack. That's why it's called 'bad' cholesterol.

Lipoprotein cholesterol rich foods leads imbalance, causing the body to make more HDL than LDL. That is why it is considered safer to buy cooking oil with less or no cholesterol. Foods rich in trans-fatty acids (like margarine and butter) promotes the formation of LDL, while a diet rich in fiber (root vegetables, fruits) and omega-3 fatty acids (fish, flaxseed oil) and Vitamin B3 promotes good cholesterol. So let's go slow on fries, and eat more carrots!
Foods rich in fiber (root vegetables, fruits) and omega-3 fatty acids (fish, flaxseed oil) and Vitamin B3 promotes good cholesterol.

A bad feature is the abuse of steroids or cholesterol 'doping'. When there are high levels of testosterone in the blood, the body gains more stamina. Steroid molecules Much has been made of cholesterol that mimics the function of testosterone, such as androstendione. It's called Improving Performance Drugs (PEDs) If an athlete injects ped into the blood stream, he experienced a temporary increase stamina, which can help beat other athletes in a competition.

However, many dangers. PEDs are illegal in all sports competitions. Second, they can cause permanent damage to the body. They increase LDL, reduced immunity against infectious diseases and creates a higher risk of cancer or heart attack.