KOMPOSISI DAN SIFAT BAHAN PANGANWaterProteinCarbohydrateLipida Vitamin &Mineral Komponen Alami:Komponen Tambahan:Emulsifier Antioxidant Preservative Thickener Sweetener Etc. MUTU & KEAMANANPANGANEnzimAntioksidanAsamPigmenCitarasa

KARBOHIDRAT PENDAHULUAN KARBOHIDRAT DALAM BAHAN PANGAN KLASIFIKASI DAN STRUKTUR KIMIA REAKSI KIMIA KARBOHIDRAT SIFAT FUNGSIONAL KARBOHIDRAT

1. PENDAHULUAN75 % of Biological World80 % of the Calorie Intake of humankind75 80 % starchIn USA : Composition of Calorie IntakeCarbohydrate : 46% 47 % Starch52% SucroseFats : 42%Protein : 12%Rumus Umum : Cx(H2O)yModifikasi struktur Sifat Fungsional

2. KARBOHIDRAT DALAM BAHAN PANGANKarbohidrat utama dalam :animal : glucose, glycogenmilk: lactose plant : cellulose, starchseaweed: alginate, carrageenan, agar

2. KARBOHIDRAT DALAM BAHAN PANGAN

FoodSugar (%) Coke Crackers Ice Cream Orange Juice Cake (dry mix)912181036

Sugar in Fruits :

FruitFree Sugar (%)GlucoseFructoseSucrose Apple Grape Peach Pear Strawberry1.176.860.910.952.096.047.841.186.772.403.782.256.921.611.03

Sugar in Vegetables:

VegetablesFree Sugar (%)GlucFrucSuc Broccoli Carrot Cucumber Spinach Sweetcorn Tomato0.730.850.860.090.341.120.670.850.860.040.311.340.424.240.060.063.030.01

Sugar in Legumes :

LegumesFree Sugar (%)GlucFrucSuc Snap bean Lima Bean Pea1.080.040.321.200.080.230.252.595.27

Sugar in Fruits (per 100 gram)Sumber : Food and Nutrition Encyclopedia (1994) *) Daftar Analisis Bahan Makanan (1992)

Macam BuahJumlah Gula (%)Jenis Gula (g)Energi (kcal)GlucFrucSuc Kurma Pisang Kismis Apel Nanas Anggur Pear Jeruk Manis Mangga Blewah48.819.614.211.010.69.38.78.57.46.524.95.2-1.22.34.82.52.5-1.123.95.9-6.01.44.35.01.8-1.3-8.514.23.86.90.21.24.27.44.127198 *)28964 *)57 *)686151 *)73 *)30

3. KLASIFIKASI DAN STRUKTUR KIMIAPhotosynthesisCarbohydrates are synthesised in green plants by photosynthesis. Solar energy is absorbed by the green pigment in plants, chlorophyll. This energy is used to drive many enzyme-catalysed processes. The overall effect is to reduce carbon dioxide to carbohydrates and oxidise water to oxygen:LingkunganTanamanLingkungan

Energi dan Analisis KH. Tiap molekul heksosa akan membebaskan 675 Kal dalam reaksi kebalikan dari fotosintesis. 1 mol Heksosa menjadi CO2 dan H2O menghasilkan energi 675/180 = 3,75 Kal per gram

. Pembakaran sukrosa memberikan 3,95 Kal per gram. Efisiensi pencernaan sukrosa 98% shg kalori yg dihasilkan untuk tubuh dari 1 gr sukrosa : 3,95 x 0,98 = 3,87 Kal per gram

Energi dan Analisis KH. Bila tjd polymerisasi, bbrp molekul heksosa membentuk homoglikan (Exp. Pati (C6H6O5)x dihasilkan 4,18 Kal per gram. Efisiensi pencernaan pati 98-99% maka 1 gr KH : 0,98 x 4,18 = 4,0 Kal

. Analisa KH dg proximate analysis : analisa dimana kandungan KH termasuk SK diketahui mll perhitungan% KH = 100% - % (Protein+Lemak+Abu+Air)

. Analisa dg Carbohydrate by Difference : penentuan KH dlm makanan scr kasar dan hasilnya dicantumkan dlm Daftar Komposisi Bahan Makanan

CARBOHYDRATE Cx(H2O)yMonosaccharidesPOLYSACCHARIDESDisaccharidesHexose (C-6)Pentose (C-5)D-GlucoseD-GalactoseD-MannoseD-FructoseXyloseArabinoseRiboseSucrose (a+d)Lactose (a+b)Maltose (a+a) -> aCellobiose (a+a) ->bOligosaccharidesRafinose (b+a+d)Stachyose (b+b+a+d)VerbacoseCellulose (-> a)Starch (-> a)Chitin Agar (->b)Carrageenan (->b)Alginat

POLYSACCHARIDESSTARCHNON-STARCHPOLYSACCHARIDESAlginateCarrageenanAgarFurcellaranDaratan:CellulosePectinPerairan:ChitosanGumLainnyaLainnya

Struktur KimiaCOHHCCCCCHHHHOOHOHHHOHOH=OHHOOHOHOHHCH2OHHHa-D-Glukosa123456123456a-D-Glukosa(Aldosa)(Aldohexose)Gugus Karbonil (CO)Gugus Aldehid (CHO) = gugus reduksiAtom C asimetris terjauh dari karbonil (CO)Sebagai dasar penamaan D (OH dikanan) dan L (OH di kiri)HOH1bAtom C Chiral

Struktur Kimia

Struktur KimiaCOHHCCCCCHHHHOOHOHHHOHOH=OHHOOHOHOHHCH2OHHHa-D-GlukosaKonfigurasi Haworth123456123456Aldehydo-D-Glukose

COHHCCCCCHHHHOOHOHHOHHOH123456a-D-Glucopyranosa

Struktur KimiaCOHHCCCCCHHHHOOHOHHHOHOH=123456a-D-Glukosa(Aldosa)Gugus Karbonil (CO)Gugus Aldehid (CHO) = gugus reduksiCOHHCCCCCHHHHOOHOHHHOHHOH123456HReduksiSorbitol Na-Amalgam Li-Al-hydride hydrogenation

Struktur KimiaCOHHCCCCCHHHHOOHOHHHOHOH=123456a-D-Glukosa(Aldosa)(Hexose)(C6H12O6)Gugus Karbonil (CO)Gugus Aldehid (CHO) = gugus reduksiCOHCCCCCHHHOOHOHHHOHHOH123456H=a-D-Fruktosa(Ketosa)(Hexulose)(C6H12O6)Gugus KetonROHCCHO=R = H AldehydeR = CH2OH KetonSaccharose group

Struktur KimiaCarbonyl group

Keton Aldehid Aldehydes are readily oxidised to carboxylic acids:If copper (II) (blue Cu2+) is used as the oxidising agent it is converted into copper (I) which forms red copper oxide (Cu2O) as a precipitate. This is how Benedicts reagent and Fehlings solution are used to test for aldehydes and reducing sugars.

Struktur Kimia

OHHOOHOHOHHCH2OHOHHOOHOHOHHCH2OHOHOHOHOHOHHCH2OHHHHHHHa-D-Glukosaa-D-Manosaa-D-GalaktosaOOHCH2OHOHCH2HOHOHH123456123456a-D-FructoseHMONOSAKARIDAaaaa

OHHOOHOHOHCH2OHHHa-D-Maltosa(Glukosa-a-(14)-Glukosa)OHOHOHOHHCH2OHHHDISAKARIDAa-D-Glukosaa-D-Glukosa terdiri atas 2 molekul glukosa dari hydrolysis pati oleh b-amylase gula reduksi

OLactosaGalaktose-b-(14)-Glukosa)OHOHOHOHHCH2OHHHDISAKARIDAa-D-Glukosa terdiri atas Galaktosa dan Glukosa terdapat pada susu : Mamalia : 2 8.5% Cow and Goat : 4.5 4.8% Human : 7 % gula reduksiOHOHOHOHHCH2OHHHa-D-Galaktosa

SukrosaGlukosa-a-(12)-Fruktosa)DISAKARIDA terdiri atas Glukosa dan Fruktosa terdapat pada cane atau beet gula non-reduksi table sugarOHHOOHOHOHCH2OHHHa-D-GlukosaOOHCH2OHOHCH2OHOHH123456a-D-FructoseH

Jenis Oligosakarida yang banyak terdapat di AlamOligosakarida adl polimer dg derajat polimerisasi 2 10 dan biasanya larut dalam air

Derajat PolimerisasiHomo-Reduktif (gugus OH)Homo-Non ReduktifHetero-ReduktifHetero-Non Reduktif2Selobiosa Isomaltosa GentibiosaTrehalosaLaktosa Laktulosa Maltulosa MelibiosaSukrosa3MaltotriosaRafinosa4MaltotetrosaStakiosa5MaltopentosaVerbakosa6 - 10MaltoheksaDekstrinSchardingerAjukosa

POLISAKARIDADalam bhn makanan berfungsi :sbg penguat tekstur (selulosa, hemiselulosa, pektin, lignin)-sbg sumber energi (pati, dekstrin, glikogen, fruktan)

PATI Homopolimer glukosa dg ikatan -glikosidikTdr dr fraksi yg dipisahkan dg air panas :a/ fraksi terlarut (AMILOSA)b/ fraksi tidak larut (AMILOPEKTIN)Semakin kecil amilosa / semakin tinggi amilopektin Nasi semakin lengketBeras ketan (amilosa 1-2%), Beras biasa (amilosa > 2%)Nasi /beras terbagi 4 gol : (1) amilosa tinggi (25-33%); (2) amilosa menengah (20-25%) ~ orang Indonesia, Mlaysia, Philipina, Thailand; (3) amilosa rendah (9-20%) ~ orang Jepang & Korea; (4) amilosa sangat rendah (

Granula pati dari beberapa komoditi (Martin, 1979)

GELATINASIBila pati mentah dimasukkan air dingin, granula pati menyerap air (makssimal 30%) & membengkak Peningkatan volume granula pati dalam air (suhu 55-65C. Granula pati dibuat membengkak tapi tdk bisa kembali pd kondisi semula : GELATINASISuhu gelatinasi (diukur dg viskosimeter & polarized microscope) pada jagung 62-70C, beras 68-78C, gandum 54,5-64C, kentang 58-66C, tapioka 52-64C

Granula pati mempunyai sifat merefleksikan chy terpolarisasi shg di bwh mikroskop terlihat kristal hitam putih : sifat BIREFRINGENT

Kisaran suhu yg menyebabkan 90% butir pati dlm air panas membengkak shg tdk kembali lagi ke bentuk normal : BIREFRINGENT END POINT TEMPERATURE (BEPT)

BEPT rendah 55-69CBEPT medium70-74CBEPT tinggi 75-77C

Proses kristalisasi kembali pati yang telah mengalami gelatinasi : RETROGRADASI

Keluarnya atau merembesnya cairan dari suatu gel dari pati : SINERESIS

Enzim yg dapat menghidrolisis pati : -amilase, -amilase & fosforilase

Bagian pati yang tidak terurai menjadi residu karena -amilase tidak mampu menghidrolisis amilopektin di luar batas (hanya 60-70%) : -amilase limit dextrin

Pati + PO43-fosforilase-D-glukosa-1-fosfat

OHOHOHCH2OHHOHOHOHHCH2OHHHCELLULOSEa-D-Glukosaa-D-GlukosanPOLISAKARIDAikatan-b-(14)-Glikosidik)OHOHOAABBO1421441

POLISAKARIDA

POLISAKARIDA

REAKSI-REAKSI KARBOHIDRAT HYDROLYSIS NON-ENZYMATIC BROWNINGAs shown in Table 4.29, the C1 and Cx factors, which were found to be endo- and exo-1,4--glucanases respectively, hydrolyze cellulose to cellobiose. Since the C1 factor is increasingly inhibited by its product, a cellobiase is needed sothat cellulose breakdown is not rapidly brought to a standstill. However, cellobiase is also subject to product inhibition. Therefore, complete cellulosedegradation is possible only if cellobiase is present in large excess or the glucose formed is quickly eliminated.

REAKSI-REAKSI KARBOHIDRAT HYDROLYSIS : Pembuatan HFCS (High Fructose Corn Syrup)POLYSACCHARIDESAcid TreatmentHeat TreatmentEnzyme Treatment123PRODUCTSHFCS

4. REAKSI-REAKSI KARBOHIDRAT HYDROLYSIS : Fermentasi TapeBAHAN BAKUFermentation Jenis Mikrobia Suhu WaktuPRODUCTS Ketela Pohoh Ketan Tape singkong Tape KetanStarchGlucoseAlcoholAcid

BROWNING ENZIMATIS NON-ENZIMATIS Reaksi Enzimatis Dipengaruhi oleh : Substrat Enzim Suhu Waktu Reaksi Maillard Karamelisasi Reaksi Gula & Protein Dipengaruhi oleh : Jenis Gula Suhu Waktu Pemanasan Gula Dipengaruhi oleh : Suhu Waktu Ascorbic acid oxidation

BROWNING Reaksi Maillard Ilmuwan Perancis : Louis Maillard (1912) glucose + glycine Carbonyl Amine Reaction action of amino acids/protein on reducing sugars Related to aroma, taste and color Roasting of coffee and cacao beans, baking of bread and cakes, toasting of cereals, cooking of meats

BROWNING REDUCINGSUGARAMINOACIDCARBONYLAMINEMelanoidins (Brown Pigments) Dipengaruhi oleh : Jenis Gula Asam Amino pH Suhu Katalis Kadar Air5-Hydroxymethyl-2-Furfuraldehyde(HMF)

REAKSI MAILLARDReaksi antara gula pereduksi dan Protein (asam amino)Dipengaruhi oleh suhu, waktu dan jenis gulaMenghasilkan warna coklat Prosesnya berlangsung pada suasana basaProses yang terjadi pada reaksi maillard:Gugus karbonil pada gula menghasilkan N-glukosamin dan airGugus glukosamin yang tidak stabil mengalami pengaturan kembali membentuk ketosaminKetosamin mengalami proses lanjut:Memproduksi air dan reduktonMenghasilkan diasetil, aspirin, pyruvaldehid, dan ikatan hidrolitik lainMembentuk melanoidin.

MAILLARD REACTION (i) Initial stage (colourless)a. sugar-amine condensationb. Amadori rearrangement(ii) Intermediate stage (colourless to yellow)c. sugar dehydrationd. sugar fragmentatione. amino acid degradation(iii)Final stage (highly coloured)f. aldol condensationg. aldehyde-amine polymerisation, formation of heterocyclic nitrogen compounds.

Maillard Reaction Fig. 1. Effect Temperature on the reaction rate of D-Glucose with DL-Leucine

Maillard Reaction Fig. 1. Effect pH on the reaction rate of D-Glucose with DL-Leucine

BROWNING REACTIONSSUCROSESUCROSE +FRUCTOSESUCROSE +LACTOSEMaillard Reaction : (Lysine + Sugars)

BROWNING NON ENZIMATIS : MAILLARDProduk : Bakpia

CARAMELIZATIONCaramelization is defined as the thermal degradation of sugars leading to the formation of volatiles (caramel aroma) and brown-colored products (caramel colors). The process is acid or base catalyzed and generally requires temperatures > 120 oC at 9

TEKNOLOGI KARBOHIDRATSUMBERKARBOHIDRATTEKNOLOGIPROSESCARBOHYDRATE-BASEDPRODUCTKetela PohonBeras KetanJagungGandumTape Ketela PohonTape KetanHFCS (High Fructose Corn Syrup)4. Karamel5. Candy6. Modified (CMC)AsamBasaPanasEnzimatisMikrobiologis

SIFAT FUNGSIONALSWEETNESS & SWEETENERSHYGROSCOPICITYReduced Aw PreservativeAdsorbent Baby care productsMoisture Beauty care productsTEKSTURAL CONTRIBUTIONRigidity : RotiViscosity: Saus

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