Kuliah keIX m k SATUAN PROSES FLAVOR PERISA

Kuliah ke-IX m. k. SATUAN PROSES FLAVOR (PERISA) DEPARTEMEN TEKNOLOGI INDUSTRI PERTANIAN FAKULTAS TEKNOLOGI PERTANIAN INSTITUT PERTANIAN BOGOR 2011

TIK Memberikan pengetahuan mengenai proses konversi yang dapat terjadi pada bahan yang mengandung flavor (perisa) dan aplikasinya di Agroindustri Pokok Bahasan Proses Konversi Pada Bahan Yang Mengandung Flavor Sub Pokok Bahasan Substansi Rasa, Sumber Flavor, Flavor dan Aroma dalam Produk Hasil Pertanian (Bawang, Kopi, Teh)

Definition of Flavor Integrate response to a complex mixture of stimuli primarily on the senses of smell and taste, but also on those associated with sight (color and appearance), tactile sensation (texture and mouth feel) and pain (pungency) Flavor is one of the important qualities of foods which are decisive in the selection, acceptance, and ingestion of a food.

Stimulus Senses Sensory Response Taste Food Flavor Odor

Pada dasarnya lidah hanya mampu mengecap (taste) empat jenis rasa: yaitu pahit, asam, asin dan manis. Substansi rasa : manis, pahit, asam, dan asin Manis grup hidroksi (molekul gula), sakarin, kloroform Pahit pahit dan manis berasal dari kelompok yang sama, dengan perbedaan tergantung pada stereokimia molekul stimulus Contoh : -Asam amino D-isomer manis, L-isomer pahit -Sakarin manis, tapi terlalu banyak menyebabkan rasa pahit -Fenil tiokarbamida, Kreatin -Alkaloid quinone, kafein, teobromin Asin rasa asin klasik : Na. Cl dan Li. Cl Alternatif : garam K dan ammonium Asam ion hidronium (H 3 O+)

Flavor enhancer berkontribusi terhadap rasa lezat suatu makanan Contoh : - MSG (mono sodium L-glutamat) - 5’IMP (5’ inosin monofosfat) Astringency fenomena seperti rasa kesat, rasa kering di mulut, (seperti pengeringan jaringan mulut) Asosiasi dari tanin atau polifenol dengan protein dalam saliva Contoh : tanin pada teh Pungency sensasi rasa pedas dan tajam contoh : cabe (capsaicin), merica (piperine), jahe (gingerole) Cooling sensasi cooling (dingin) terjadi akibat kontak bahan di hidung dan jaringan mulut contoh : pippermint, spearmint, wintergreen, mentol, camphor

Development of Flavor Substances a. Flavor substances formed during normal plant & animal metabolism. *Plant remain in situ when the plant is harvested (example : essential oils, fruit and vegetable flavors). - Fruit flavor develops during ripening periode - Vegetables flavor develops during cellular disruption b. Flavoring components resulting from enzyme-catalyzed reactions (e. g. enzyme-modified dairy products : butter, cheese etc) c. Flavoring constituent produced as a result of microbiological action/fermentation (e. g. wines, dairy products, tea) d. Flavor resulting from heat processing or cooking (e. g. cooked meat flavors, roasted coffee)

a 1. Formation of flavor components in Vegetables Fatty acid Carbohydrate Amino acid metabolism Nonvolatile Precursor Linoleic. Linolenic acid Thioglucosinolate Cystein. Methyl. Sulfoxides (C methionine -S) Precursor-splitting Enzyme Lipoxygenase Thioglucosidase C-S-lyase None (heating) Carbonyls Alcohols Oxo-acids Isothiocyanates Polysulfides CH-S-CH 3 Nitrilles Alkyl. Thiocyanates thiosulfinates etc

a 2. Diagram Biosintesis Senyawa Flavor Buah-buahan Karbonil Alkohol Asam okso Thiosianat Nitril Isothiosianat Alkilthiosulfinat Polisulfida ASAM LINOLEAT ASAM LINOLENAT THIOGLUKOSINOLAT SISTEIN SULFOKSIDA Lipid Karbohidrat Protein β-oksidasi Asam alifatik Alkohol Ester Karbonil Lakton Asetil Ko-A Siklus asam Mevalonat Monoterpen Seskuiterpen Siklus Asetat Asam shikimat Mono substitute Phenol C 6 C 1 Fenol Kresol Orsinol C 6 C 3 Fenol Asam sinamat Eugenol Safrol Polifenol Flavonoid

b. Flavouring substances produced with Enzymes Product Butyric acid Caproic acid Acetaldehyde Substrate Butter fat Ethanol Enzyme Lipase Alcohol dehydrogenase Geranial Geraniol Cinnamic alcohol Methanethiol Capric acid Cinnamic aldehyde Methionine Butter fat Alcohol dehydrogenase Methioninase Lipase

c. Flavouring Substances produced by Microbial Fermentation Microorganism Lactococcus species Leuconostoc species Product Diacetyl Pseudomonas species 3 -Isopropyl-2 -methoxy pyrazine Streptococcus lactis Trichoderma viride Bacillus subtilis Corynebacterium glutamicum Methyl butanol 6 -pentyl-α-pyrone Tetramethyl pyrazine Aspergillus oryzae 1 -octene-3 -ol (mushroom aroma)

d. Flavor Formation During Thermal Processing (Cooking) Nonenzymatic Browning (Maillard browning, caramelization) e. g. baked bread, steak, freshly brewed coffee or chocolate *Maillard Browning : Reaction between carbonyls (reducing sugars) and amines (amino acids/proteins) melanoidin & pyrazine (largest contribution to flavor of chocolate) Formation of Flavor Compound via Maillard Reaction : Aliphatic aldehydes, ketones, diketones & lower chain length fatty acids *Caramelization : sugars thermally decomposed at >1500 C, more rapidly at at high p. H

Deep Fat Fried Flavor : a. Hydrolysis of triglycerides (reaction between triglyceride with water) a. Oxidation of unsaturated fatty acids a. Pyrolysis reaction (>2000 C, overheated) acrolein (burnt fat : glycerol acrolein)

Contoh Flavor dan Aroma dalam produk Hasil Pertanian Bawang Putih S-(2 -propenil)-L-Sistein Sulfoksida =Alliin (prekursor, tidak berbau) allinase Diallyl thiosulphinate (Allicin) When fresh garlic is chopped or crushed, the enzyme allinase converts alliin into allicin which is primarily responsible for the aroma of fresh garlic. Allicin : Ø provides flavor, pungency and bioactive. Ø help prevent heart disease (including atherosclerosis, high cholesterol, and high blood pressure) and cancer

*Pembentukan aroma pada Bawang Putih O O NH 2 +H 2 O-2 NH 3 2 H 2 C=CH-CH 2 -S-CH 2 -CH-COOH H 2 C=CH-CH 2 -S-S-CH 2 -CH=CH 2 -2 H 3 C-CO-COOH S-Allyl-L-cysteine sulfoxide Diallyl thiosulphinate (Allicin) (Alliinase) (Aliin: prekursor tdk berbau) H 2 C=CH-CH 2 -S-S-CH 2 -CH=CH 2 Diallyl disulphide H 3 C-S-S-CH 2 -CH=CH 2 Methylallyl disulphide Other products The sulfur compound allicin, produced by crushing or chewing fresh garlic produces other sulfur compounds : allyl sulfides, ajoene, and vinyldithiins.

When a cell is broken by chopping, chewing, or crushing, enzymes stored in cell vacuoles trigger the breakdown of several sulfur-containing compounds stored in the cell fluids. The resultant compounds are responsible for the sharp or hot taste and strong smell of garlic. Diallyl disulfide is believed to be an important odour component. Allicin has been found to be the compound most responsible for the "hot" sensation of raw garlic. The process of cooking garlic removes allicin, thus mellowing its spiciness

Kopi Flavor kopi kafein, asam, senyawa fenol, dan senyawa volatil hasil dari penyangraian biji kopi (200 -250 o. C, 20 -30 menit). Flavor asam tergantung senyawa asam klorogenat, asam quinat Selama penyangraian : Karbohidrat (gula) karamelisasi Asam amino pirolisis Tanin bahan fenolik volatil

Tambahan Info Coffee Bean Roasting (approximately 200°C) : Caramelization occurs as intense heat breaks down starches in the bean, changing them to simple sugars that begin to brown, changing the color of the bean. Sucrose is rapidly lost during the roasting process and may disappear entirely in darker roasts. During roasting : Ø aromatic oils, acids, and caffeine weaken, changing the flavor Øat 205°C, other oils start to develop. One of these aromatic oil is caffeol, created at about 200°C, which is largely responsible for coffee's aroma & flavor.

Teh Tea contains : - Catechins, a type of antioxidant (highest in concentration in green tea, while black tea has substantially fewer due to its oxidative preparation) - Theanine - the stimulant caffeine, - small amounts of theobromine, theophylline and fluoride

Tambahan Info Tea Processing - Leaves of Camellia sinensis soon begin to wilt and oxidize if not dried quickly after picking. - The leaves turn progressively darker as their chlorophyll breaks down and tannins are released. This process, enzymatic oxidation, is called fermentation in the tea industry, although it is not a true fermentation: it is not caused by microorganisms, and is not an anaerobic process. The next step in processing is to stop the oxidation process at a predetermined stage by heating, which deactivates the enzymes responsible. With black tea this is done simultaneously with drying.

Teh : Pengaruh proses terhadap aroma teh Tipe proses Produk utama Oksidasi lipid tidak jenuh - cis-3 -heksenol - trans-2 heksenal Degradasi asam amino Aldehid, sebagian berubah menjadi alkohol Hidrolisis glikosida terpene Linalool, geraniol Degradasi karotenoid Monoterpen

Flow Diagram of Chocolate Production Senyawa : Theobromin (stimulating) & tannin (color & taste) Step 1: cocoa beans Step 2: shell and nibs Step 3: cocoa powder Step 4: plain chocolate

Flavor Daging Thiazole flavor daging rebus 2 -metil-3 -furantiol flavor daging bakar Beberapa bahan yang biasa digunakan untuk meningkatkan flavor daging : - Hidrolisat protein tanaman/HVP - Glukosa - Otolisat khamir (yeast extract) - Arabinosa - Lemak hewan tertentu - 5’-ribonukleotida - Tepung Telur ayam - Metionin - Gliserol - MSG - Glutatione - Thiamin (Vit. B 1) - Sistein

Ø The Maillard reaction occurs when the denatured proteins on the surface of the meat recombine with the sugars present. Ø The combination creates the "meaty" flavor and changes the color. For this reason, it is also called the browning reaction. The Maillard reaction occurs most readily at around 300° F to 500° F. Ø When meat is cooked, the outside reaches a higher temperature than the inside, triggering the Maillard reaction and creating the strongest flavors on the surface. http: //www. exploratorium. edu/cooking/meat/INT-what-makes-flavor. html

Ingredients of Flavouring consist of : • 1. Flavouring ingredients : Flavouring substances natural, natur-identical, artificial • 2. Non-flavouring ingredients : Flavor adjunct, flavor enhancer

1. Flavouring Ingredients Flavouring Substances are defined chemical component with flavouring properties, not intended to be consumed as such and categorized as : a. Natural Flavouring Substances : defined substance obtained by appropriate physical, microbiological, or enzymatic processes from foodstuff or material of vegetable or animal origin as such (natural state) or after processing by food preparation processes. Can not contain any nature-identical or artificial flavoring substances

Natural Flavoring “The term “Natural Flavoring” or “Natural Flavor” means : essential oil, oleoresin, essence or extractive, protein hydrolysate, distillate, or any product of roasting, heating or enzymolysis, which contains the flavoring constituents derived from natural sources : spice, fruit, or fruit juice, vegetable or vegetable, edible yeast, herb-plant material, meat, seafood, poultry, eggs, dairy products, or fermentation products whose significant function in food is flavoring rather than nutritional”

- b. Nature-Identical Flavouring Substances : flavouring substances obtained by synthesis or isolated through chemical processes from a natural aromatic material and chemically identical to a substance present in natural products intended for human consumption, either processed or not • In general are members of chemical groups like aliphatic alcohol, aldehydes, ketones, acetals, acids, esters, heterocyclics, phenolesters, sulphides, thiols. • Manufactured mostly by esterification, oxidation, or Grignard reaction from essential oils or terpene fractions thereof, fats and mineral oils derivatives.

c. Artificial Flavouring Substances : flavouring substances, not yet identified in a natural product intended for human consumption, either processed or not. These are typically produced by fractional distillation and additional chemical manipulation naturally sourced chemicals or from crude oil or coal tar. Vanillin www. fantastic-flavour. com/natural_vanilla

Artificial Flavouring Substances : Example • Vanillin (4 -hydroxy-3 -methoxybenzaldehyde): starting material is guaiacol • Ethyl vanillin : starting material is guaiene Vanillin www. fantastic-flavour. com/natural_vanilla

2. Non Flavouring Ingredient : Flavour adjunct : food additives and food ingredients necessary for the production, storage and application of flavouring as far as they are non-functional in the finished food • • • Example : Solvent : water, glycerol, triacetine, ethanol, propylene glycol (PG), vegetable oil, triethyl citrate, benzyl alcohol Carrier : modified starch (maltodextrine), lactose, gelatin Emulsifier/stabilizer : mono/diglycerides, gelatine Colorant Processing aids (enzyme) : microbial or animal derived

Flavour enhancer : substance with little or no odour at the level used, the primary purpose of which is to increase the flavour effect of certain food components well beyond any flavour contributed directly by the substance itself • Example : - MSG - Ribotide (I+G) - Sugar, salt & vinegar

Example of Vegetable Based Material : • Plant extract (e. g. fruit juices, essential oil, oleoresin, etc. ) • HVP (hydrolyzed vegetable protein) soy protein hydrolyzed by acid or enzyme • Flavouring substances isolated from essential oil (e. g. anethol, benzaldehyde, eugenol, citral, dimethyl sulfide, etc. ) • Dried spices & herbs

Example of Animal Based Materials : • • Meat & fat (fresh, dried, extract) Milk & its derivatives Fatty acids Amino acids (e. g. cysteine, cystine (can be from human hair/feather) & phenylalanine ) www. tradeindia. com/. . . / Meat-Extract. Paste. htm

• Animal secretion : ikan paus - Ambergris or ambra (intestinal tract of the sperm or cachalot whale) - Civet absolute (odorous glandular secretion of male and female civet) Civet (Kesturi) - Musk absolute (glandular secretion of the male musk deer, found in an internal pouch located under the skin of the abdomen) musk deer identics. tripod. com/parfum/bahan_aromatis. htm

Jenis Flavor Berdasarkan sumber dan proses pembuatannya : 1. Flavor natural/alami 2. Flavor Natural identical (diolah dari bahan alami untuk menghasilkan flavor sintetis). 3. Flavor Artifisial/Sintetis (buatan) Flavor natural/alami dibuat atau diekstraksi dari bahan-bahan alami, misalnya rasa bawang yang diambil dari ekstrak bawang, rasa ayam yang diperoleh dari sari ayam, rasa udang yang berasal dari tepung udang, dll

Perisa natural identical disusun dari bahan-bahan alami untuk menghasilkan rasa yang identik dgn yg ada di alam misalnya turunan dari minuman keras yang bisa disintesa menjadi berbagai perisa buahan. Contohnya fussel oil yang merupakan produk samping dari minuman keras, bisa digunakan sebagai bahan penyusun perasa stroberi, leci, dan nanas. Sebenarnya bahan-bahan tersebut adalah bahan alami, tetapi kemudian direaksikan dengan bahan-bahan lainnya dan menghasilkan rasa tertentu yang dikehendaki.

Perisa buatan/sintetis (artifisial) dihasilkan dari bahan-bahan sintetis/reaksi kimia, contohnya sintesis bahan-bahan kimia yang berasal dari turunan minyak bumi. Contoh • butil cinamaldehid yang memiliki rasa mirip dengan bunga (melati dan lili) • butil butirat yang memiliki rasa mirip buah-buahan pir dan nanas • Berbagai asam amino yang bisa mirip rasa daging atau ayam.

Flavor terdiri dari berbagai jenis Salah jenis molekul dasar yang dapat dimodifikasi untuk membentuk komponen aroma yang berbeda, contohnya adalah dicyclopentadiene (DCPD)

CONTOH KOMPONEN PENYUSUN FLAVOR

FLAVOR CREATION : 2 cara/pendekatan 1. Metode tradisonal untuk menciptakan formula konstituen flavor utama yang diketahui lalu diatur nuasanya dgn menambahkan bahan flavor dgn karakter odor/flavor yg diketahui tergantung pengalaman flavoristnya 2. Pendekatan ilmiah, menciptakan formula flavor menggunakan hasil analisis dg Gas Kromatografi/alat lain menghasilkan profil flavor, tapi ada komponen flavor yang tak terdeteksi ) disebabkan error /keterbatasan alat saat analisis terbaik kombinasi keduanya

FLAVOR BREAKDOWN Flavor break down into : flavor (character, contributory and differential) + diluent Character Impact : when smelled, that are clearly reminiscent of the named flavor. This could be a pure flavor chemical ( e. g citral for lemon) or a natural material (e. g fenugreek for maple). See Table 1. Flavor Contributory : these components help develop the named flavor, They have a character similar to that of the named flavor (e. g. oil of tagette for apple, orris root for raspberry and ethyl butyrate for grape) Flavor Differential : these components contribute different unique notes to the flavor (e. g. peppermint for vanillin flavor, jasmine for strawberry flavor, menthol for flavor butterscotch)

Table 1. Character Impact Apple Ethyl 2 -methylbutyrate Iso amyl acetate Banana Iso amyl acetate Butter Diacetyl Caramel 2, 5 dimethyl-4 hydroxy furanone Cherry Benzaldehyde Cinnamon Cinnamic aldehyde Coconut Gamma nona lactone Delta octalactone Clove eugenol Jasmine Benzyl acetate

Table 1. Character Impact (cont. ) Lemon citral Mushroom 1 -octen-3 -ol Peach Gamma undecalactone Peanut 2, 5 -dimethyl pyrazine Peppermint Menthol Seafood pyridine Piperidine Trimethyl amine Smoke Guaiacol 2, 6 -dimethoxyphenol Strawberry Ethyl methylphenylglycidate Ethyl maltol Tomat Isobutyl thiazole Vanilla vanillin

Diluent = flavor solvent Flavors are seldom 100 % active components , but more likely only 10 -20 %. This is because the individual flavor contituent may not be mutually soluble. A solvent may therefore be required to keep the flavor from precipitating or undergoing phase separation. The solvent also adds some bulk, which may be desirable in term of manufacturing (i. e. a larger volume to weight or distribute in a food product) water, glycerol, triacetine, ethanol, propylene glycol (PG), vegetable oil, triethyl citrate, benzyl alcohol Can be added with other flavor adjuct and or flavor enhancer

FLAVOR MANUFACTURING 1. Raw Materials Handling : Comminution, sieving, extraction with solvent, pressing, distillation (direct, steam, vacuum, azeotropic) and sterilization (gas, radiation) 2. Liquid Flavor Production : Blending and compounding, clarification (filtration, centrifugation), emulsification, homogenization, pasteurization and preservation 3. Dry Flavor Production : Dehydration, adsorption, spray-drying, microencapsulation, powder blending

Keamanan Flavor • Keamanan produk (product safety) dan teknik evaluasi keamanan perlu diperhatikan , khususnya dalam penggunaannya didalam bahan pangan. Evaluasi keamanan bagi senyawa flavor dimulai tahun 1960, di AS terhadap bahan a Aditif atau Bahan Tambahan Pangan. • Senyawa yang terbukti aman oleh para pakar mendapat Status GRAS (Generally Recognized as Safe) Di Amerika, evaluasi senyawa flavor dilaksanakan oleh FEMA (The US Flavor and Extract Manufacturer's Association). • Di Eropa, kegiatan evaluasi keamanan senyawa flavor dilakukan oleh Council of Europe (Co. E). Co. E mempublikasikan suatu daftar yang berisi senyawa flavor serta sumber alam dari flavor yang disebut "Blue Book".

Bahan Baku (bagian tumbuhan/tanaman/hewan) Pre-Treatment (Sortasi, Pencucian, Pembersihan, Pengecilan ukuran, dll) Pemisahan komponen/bahan aktif (Ekstraksi, Destilasi, Filtrasi, Separasi, dll) Kondensasi Pengeringan Evaporasi Cairan Bubuk Konsentrat Diagram alir proses produksi flavor

PRODUK FLAVOR

Aplikasi Produk Flavor pada Industri Penggunaan produk industri flavor dalam produk-produk pangan dan non pangan relatif sedikit namun besar peranannya dalam menentukan kualitas hasil akhir produk Produk flavor pada dasarnya merupakan, bahan baku (intermediet) dan bukan produk akhir. Contoh : Es krim dengan aneka rasa, seperti rasa coklat, vanilla, strawberry dan lainnya.

Diagram alir proses produksi es krim

Bahan baku es krim ; susu, krim, dry milk, gula, emulsifier dan berbagai jenis flavor www. wsu. edu/creamery/ferdtour 3. htm

Diagram Alir Proses Produksi Soft Drinks Flavor www. pall. com/Foodand. Bev_3658. asp

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