《食品化学》课程教学资源（英文讲义）04 Carbohydrates part2

3/2/14CarbohydratesDegreeofSweetnessPartTwoSugarRelative degree ofSweetness120Fructose70Glucose100Sucrose30-50Corn SyrupHigh-Fructose80-90Com SyrupInvert sugar syrup95(Honey)1W550,000,000lbs.ofHoneyHI-SWEETHFCSwillbemadeherenext yaraiHunter of bees,Arana,Spain 7000BCEHubingeTheoldest writtenreferenceto theuse of honeyisthoughttobeEgyptian, of about 5500BC.At that timeLowerEgypt was calledBeeLandwhileUpperEgyptwasReed Land

3/2/14& 1& Carbohydrates Part Two Degree&of&Sweetness& Sugar Relative degree of Sweetness Fructose 120 Glucose 70 Sucrose 100 Corn Syrup 30-50 High-Fructose Corn Syrup 80-90 Invert sugar syrup (Honey) 95 Honey& The oldest written reference to the use of honey is thought to be Egyptian, of about 5500 BC. At that time Lower Egypt was called Bee Land while Upper Egypt was Reed Land. Hunter of bees, Arana, Spain 7000 BCE

3/2/14Columbus took sugarcanes toSugarcane Historyhttp://en.wikipedia.org/wiki/History_of_sugar (optional)the AmericasNew Guinea people were probably first to domesticate sugarcaneIndiapeople discovered howfo crystallizesugar 400BCSugarcane fechnology latter carried te China and ArabisTheSpanish and PortuguesestartedCrusadersbroughtsugarcanecultivafiontoEuropesugar cane growth and production inthe Americas.The English, Dutch and French latterbecame involved in the large scaleproduction of sugar as wellSugartradesource of greatwealthforBritain and theDutch(jams,candy,tea,cofee,cocoa,processedfoodsand other sweet foods)The Brifish and Dutch sent all exports ofAverage consumptionmanufactured goods to theirper person in Britaincoloniesin their shipsincrease fromand the ships returned with rum and sugar4 pounds in 1700Sugarcane tnding collapsed in the 1800s18 pounds in 1800Low prices due to competition from beet sugar 36 pounds in 1850Emancipation and end of slave trade100 pounds in 1900(1830 in England)2

3/2/14& 2& Sugarcane History http://en.wikipedia.org/wiki/History_of_sugar (optional) • New Guinea people were probably first to domesticate sugarcane • India people discovered how to crystallize sugar 400 BC • Sugarcane technology latter carried to China and Arabia • Crusaders brought sugarcane cultivation to Europe Columbus took sugarcanes to the Americas • The Spanish and Portuguese started sugar cane growth and production in the Americas • The English, Dutch and French latter became involved in the large scale production of sugar as well • Average&consump;on& per&person&in&Britain&& increase&from&& &&&4&pounds&in&1700&& &18&pounds&in&1800& && &36&pounds&in&1850&& 100&pounds&in&1900& Sugar trade source of great wealth for Britain and the Dutch (jams, candy, tea, coffee, cocoa, processed foods, and other sweet foods) The British and Dutch sent all exports of manufactured goods to their colonies in their ships and the ships returned with rum and sugar Sugar cane trading collapsed in the 1800s Low prices due to competition from beet sugar Emancipation and end of slave trade (1830 in England)

3/2/14CarbohydratesSugarBeets-RefinedSugar·Sucrose:commonchemicalname-The development of the European beetsugar industry was encouraged by the.Whitetable sugar:sucroseNapoleonic Wars. In 1807 the British began ablockade of France that prevented the importOnlytasteissweetnessof sugarcane fromthe Caribbean.:Uniform quality (99.99+% purity)-In 1813 Napoleon instituted a retaliatorySourceof nutritive energyembargo.Bythe endof the wars, over 300sugar beetmills operated inFrance and.“Empty calories"?central Europe.-Beet sugar accounts for 30% of the world'ssugarproduction.CornSyrupCornSyrup&HFCS1970's: Ordinary corn syrup (glucose solution) can be treated?Amuch cheaper sweetener obtained fromhydrolysiswith enzymestoproduce:of (corn) starches.GG:High Fructose Corn Syrups (HFCS)Itis used as a thickener,sweetener, andfor itsmoisture-retaining (humectants) properties whichkeepfoodsmoistandhelptomaintainfreshness.ThemoreFructosethe sweeter the corn syrup!Most HFCs's are about 50%glucose&50% fructose,i.e.equivalent to sucrose (??)3

3/2/14& 3& Carbohydrates& H&Refined&Sugar& • Sucrose:&&common&chemical&name& • White&table&sugar:&&sucrose& • Only&taste&is&sweetness& • Uniform&quality&(99.99+&%&purity)& • Source&of&nutri;ve&energy& • Empty&calories?& Sugar&Beets& •The development of the European beet sugar industry was encouraged by the Napoleonic Wars. In 1807 the British began a blockade of France that prevented the import of sugarcane from the Caribbean. •In 1813 Napoleon instituted a retaliatory embargo. By the end of the wars, over 300 sugar beet mills operated in France and central Europe. •Beet sugar accounts for 30% of the world's sugar production. Corn&Syrup& 1970’s& • A&much&cheaper&sweetener&obtained&from&hydrolysis& of&(corn)&starches.& • It is used as a thickener, sweetener, and for its moisture-retaining (humectants) properties which keep foods moist and help to maintain freshness. Corn&Syrup&&&HFCS& • Ordinary&corn&syrup&(glucose&solu;on)&can&be&treated& with&enzymes&to&produce:& • High&Fructose&Corn&Syrups&(HFCS)& • The&more&Fructose&the&sweeter&the&corn&syrup!& • Most&HFCS’s&are&about&50%&glucose&&&& 50%&fructose,&i.e.&equivalent&to&sucrose&(??)& G" F"

3/2/14HIGHIntensitySweeteners100-25,000timessweeterthansucrose,twogroups·Artificial, chemically synthesized sweeteners:Natural high intensity sweeteners are extractedfromvariousplants三CommonArtificial SweetenersApproved Low Calorie SweetenersPropertiesSweetnessSweetenerComparedtoSucroseAcesulfamepotassium (sunett and Sweet One)180 timesAspartameLoses its sweetness with heatMade of 2 amino acids..Aspartamephenylalanine and aspartic acidSaccharinHeat-stable300 times.Neotame(madebyNutraSweet)Bittermetallic aftertaste.SaccharinHeat stableAcesulfame200 timesSlight aftertasteSucralose (Splenda)Synergistic sweetening effect withofhersweetenersTotExtremely stableSucralose600 timesoonnSORERNONTaalrerlrePackaged with maltodextrinm(ng)NeotameNew sweetener approved in 20026000 timese()st.inUSA8e4

3/2/14& 4& HIGH&Intensity&Sweeteners& • 100H25,000&;mes&sweeter&than&sucrose,&two& groups& • Ar;ficial,&chemically&synthesized&sweeteners& • Natural&high&intensity&sweeteners&are&extracted& from&various&plants& Common&Ar;ficial&Sweeteners& Sweetener Properties Sweetness Compared to Sucrose Aspartame Loses its sweetness with heat Made of 2 amino acids, phenylalanine and aspartic acid 180 times Saccharin Heat-stable Bitter metallic aftertaste 300 times Acesulfame Heat stable Slight aftertaste Synergistic sweetening effect with other sweeteners 200 times Sucralose Extremely stable Packaged with maltodextrin 600 times Neotame New sweetener approved in 2002 in USA 6000 times Approved&Low&Calorie&Sweeteners& • Acesulfame&potassium&(Sunett and Sweet One)& • Aspartame& • Neotame&(made&by&NutraSweet)& • Saccharin& • Sucralose&(Splenda)& 8 oz Calories 100 Total Fat (g) 0 Sodium (mg) 20 Potassium (mg) 10 Total Carbohydrates (g) 28 Sugars (g) 28 Protein (g) 0 Caffeine (mg) 25 8 oz Calories 0 Total Fat (g) 0 Sodium (mg) 25 Potassium (mg) 20 Total Carbohydrates (g) 0 Sugars (g) 0 Protein (g) 0 Caffeine (mg) 24

3/2/14Saccharin (oldest)Saccharin SafetyHouse Votes to DeloyFor many years, saccharin was:1,2-benzisothiazol-3(2H)-one-1,1-dioxideThe Saccharin Bandeclared a carcinogen and itTEcan be..:300xXsweetnessofsucroseHowever, finally in 2000, the FDA.One commercial name is“Sweet‘n Low"declared it was not 'officially' acarcinogen and thus is legal touseNHSO2NHSOSucraloseAspartame(NutraSweetm)Sucralose: trade name, Splenda, is 600 X sweeter than sugar.Aspartic acid (a naturalamino acid FDA approved it in 1998 as a tabletop sweetener and nowPhenytalanine(a naturalamino acidFDAamended its regulation to allow sucralose as ageneral-purpose sweetener for all foods.H.NOCHEstesdwithmethanolimethy Sucralose tastes like sugar because it is made from tablealcohol)sugar. But it cannot be digested, so it adds no calories tofood.200x sweeter than sucroseSekenl5

3/2/14& 5& SO2 NH O Saccharin&(oldest) • 1,2HbenzisothiazolH3(2H)HoneH1,1Hdioxide& • 300X&sweetness&of&sucrose& • One&commercial&name&is&Sweet&
n&Low SO2 NH O Saccharin&Safety • For&many&years,&saccharin&was& declared&a&carcinogen&—&and&it& can&be&.& • However,&finally&in&2000,&the&FDA& declared&it&was&not&
officially&a& carcinogen&and&thus&is&legal&to& use& Aspartame&(NutraSweet™)& • Aspar;c&acid&(a&natural&amino&acid)& • Phenylalanine&(a&natural&amino&acid)& – Poten;al&problem&with&phenylketonuria &disorder& (PKU)& – Label&must&give&warning:& • Phenylketonurics:&contains& phenylalanine& • Esterified&with&methanol&(methyl& alcohol)& – Thus&this&compound&is&synthe;c&and&does&not& exist&in&nature& • 200x&sweeter&than&sucrose& Sucralose • Sucralose:&trade&name,&Splenda,&is&600&X&sweeter&than&sugar.& – FDA&approved&it&in&1998&as&a&tabletop&sweetener&and&now& FDA&amended&its&regula;on&to&allow&sucralose&as&a& generalHpurpose&sweetener&for&all&foods.& – Sucralose&tastes&like&sugar&because&it&is&made&from&table& sugar.&But&it&cannot&be&digested,&so&it&adds&no&calories&to& food.&

3/2/14AlitameCocaiColaDescription: Discovered by Pfizer, Inc., alitame (brand name Aclame') issweetener formed from the amino acids L-aspartic acid and D-alanine, and :novel amine.zeroPAORR用MRelative Sweetness: 2,000 times sweeter than sucroseCCroneStatus: A petition for alitame's use in a broad range of foods and beverages hasCokebeen filed in the U.S. Alitame is approved for use in a variety of food andOACNTbeverage products in Australia, New Zealand, Mexico and the People'sRepublic of China.Approvalalsoisbeingsought worldwide2R0ARBONATEDWATEROtherNaturally-OccurringsweetenersLCOLOR.ASPARTAME一0ORICAO.POA4beingstudiedCOPROTASMMK1%LAVORS,CITRCAOLenmAFE20L02p%HENYLKETONURRICS:CONTAINYMENYLALANINEdietcoke.comstevioside or stevia(200-250)sa2uExtracted from plants growing in Brazil &ArgentinaB38 Stevia accounts for nearly 40% of the-sweetener market in Japan and is commonused in various parts of South America.3534900004086Acesultame Kis often blended with other sweeteners (usually sucralose or aspartame). Theseplends are reputed to give a more sugar-Bke taste whereby each swoeteener masks the other'sSfertaste, andior exhibits a synergisic eftect by whichthe blend is sweeter than itsomponents.n

3/2/14& 6& Alitame& • Descrip+on:&Discovered&by&Pfizer,&Inc.,&alitame&(brand&name&Aclame™&)&is&a& sweetener&formed&from&the&amino&acids&LHaspar;c&acid&and&DHalanine,&and&a& novel&amine.& • Rela+ve"Sweetness:&2,000&;mes&sweeter&than&sucrose.&& • Status:&A&pe;;on&for&alitame's&use&in&a&broad&range&of&foods&and&beverages&has& been&filed&in&the&U.S.&Alitame&is&approved&for&use&in&a&variety&of&food&and& beverage&products&in&Australia,&New&Zealand,&Mexico&and&the&Peoples& Republic&of&China.&Approval&also&is&being&sought&worldwide.& Acesulfame K is often blended with other sweeteners (usually sucralose or aspartame). These blends are reputed to give a more sugar-like taste whereby each sweetener masks the other's aftertaste, and/or exhibits a synergistic effect by which the blend is sweeter than its components. Other&NaturallyHOccurring&sweeteners& being&studied& • stevioside&or&stevia& • (200H250x)& – Extracted&from&plants&growing&in&Brazil&&& Argen;na& – Stevia&accounts&for&nearly&40%&of&the& sweetener&market&in&Japan&and&is&commonly& used&in&various&parts&of&South&America.&

3/2/14GRASGood&GenerallyRegardedSweetasSafeOFopicanlifewaterTrop5oREB-A99%NATURALSTEVIASWEETENERCRAS-97HighestPurtySpriteBestTasteZeroCalories100e-GMP and KosherNutirwiBouros,atunePrccontheotneAgribusiness Cargill hasteamed up with Coca-Colato market anewMoreComplexcarbohydratereactionscalorie-free natural sweetenermade from the South American herbStevia.According to reports in the Wall Street Jourmal, Coca-Cola hasfiled 24 patent applications for the product, which has beententatively named Rebiana. It plans to use the sweetener in someofitsbeverages.Stevia is a member of the daisy family, and the extract is claimedto be the world's only all-natural sweetener with zero calories,zero carbohydrates and a zero glycemic index

3/2/14& 7& GRAS Generally Regarded as Safe Agribusiness Cargill has teamed up with Coca-Cola to market a new calorie-free natural sweetener made from the South American herb Stevia. • According to reports in the Wall Street Journal, Coca-Cola has filed 24 patent applications for the product, which has been tentatively named Rebiana. It plans to use the sweetener in some of its beverages. • Stevia is a member of the daisy family, and the extract is claimed to be "the world's only all-natural sweetener with zero calories, zero carbohydrates and a zero glycemic index". More&Complex&carbohydrate&reac;ons&

3/2/14EpimerizationsAldoseandH-C:=0HCmOaldose-ketoseisomerizationsHO.enolizationHOHOH1H20HO-HHO-HRR1A solution of D-glucose in 0.03.5% NaOH at 35 °CFor 100 hrC-0HC-OHHHO-givesamixture of1D-Fructose (28%), D-Mannose (3%) and D-Glucose (57%)OHOHH2OHOHHO-HLobry de Bruyn-van Ekenstein reactionRREnediolFamousreactionsElimination (strongerbase)88FennenusFoodChemitry1via enediolHC=0drorHCOH--1-HOOHH.FOH0H=0HCOH4-0HOCMoO0-0-0-0CMobHodHOOrHOCH=O-OHH-C11-0-8-8-1-0-8MConconHCOHO-HHO-C-HHiCoNH-CHOOHOHOHH-C-OHH-COHEH-CbuoinCNOHRRRRketo-enoleliminationenolketo6-Gic0etans EredelD-FucoieCoa-EnedeloMernoeFIGURE3.SIstemclatiosbigof D-ghaooc,D-mimose,aslo-fraitme viaisicamiratione.g-.2-keto-3-deoxy-D-glucoseD-glucose(3-deaxy-D-glucosulose)8

3/2/14& 8& Epimerizations and aldose-ketose isomerizations A solution of D-glucose in 0.035% NaOH at 35 °C For 100 hr gives a mixture of D-Fructose (28%), D-Mannose (3%) and D-Glucose (57%) Lobry de Bruyn-van Ekenstein reaction enoliza;on Famous reactions Elimination (stronger base) via enediol keto-enol C C C C R O OH HO H H H OH H C C C C R OH HO H H OH H OH C C C C R O OH H H OH H C C C C R O O H H OH H elimination enol-keto e.g., D-glucose 2-keto-3-deoxy-D-glucose (3-deoxy-D-glucosulose)

3/2/14More concentrated basic solutions convert sugars into variousFamousreactionstypes of saccharinic acidsElirfindtionOHHCO(strongerbase)OHH--0H--0-o+OH-OHOHOH-oHHo-HHOyH--HH,ORRR2-keto-3-deoxy-D-glucose(3-deoxy-D-glucosulose)-OH+H'OHAOHCoCoSaccharinic AcidsC-OHProlionged heating n baseHCOHCan also yield theformationXof smaller fragments Ike 3carbonH-HRFamousreactionsHMFandrelatedcompoundsheating at low pHstrongacid orbaseInBaseOHheating gives flavors and odors (aroma)5-(hydroxymethyl)-furfuralsmal, relafively voltatile compoundsHMFIn Acid (more common in foods)coloredpolymers-yellow&browncontinued dehydration (previous slide)-HMF can be found many foods which have been heated in acid-lts concentration can be used as a measure of the extent of heafing-Try the elimination, cyclization and further dehydration beginningwith D-fructose. Note that the first double bond could be between C2=Oand either C1 or C3Hu-Further heating produces colored, conjugated polymersH-C-OHH-COHCHOHCH,OH5-(hydroxymethyl)-furfuralHMF

3/2/14& 9& 2-keto-3-deoxy-D-glucose (3-deoxy-D-glucosulose) Famous reactions Elimination (stronger base) More&concentrated&basic&solu;ons&convert&sugars&into&various& types&of&saccharinic&acids& Famous reactions strong acid or base In Base heating gives flavors and odors (aroma) small, relatively volatile compounds In Acid (more common in foods) colored polymers - yellow & brown continued dehydration (previous slide) C C C C C O O H H OH H H C H2OH H OH C C C C C O O H H H C H2OH H OH O C H O OH H2C OH H O C H O H2C OH 5-(hydroxymethyl)-furfural HMF HMF and related compounds heating at low pH •HMF can be found many foods which have been heated in acid •Its concentration can be used as a measure of the extent of heating •Try the elimination, cyclization and further dehydration beginning with D-fructose. Note that the first double bond could be between C2 and either C1 or C3. •Further heating produces colored, conjugated polymers 5-(hydroxymethyl)-furfural HMF O C H O H2C OH

3/2/14-a3D-Glucose3-deoxy-glucosuloseeORoTo美美美美OHduaSeOHD-Fructose1,2 enediol2,3 enediolOuOeimORaH,o+-aitooduaIBMs2,3 enediolIn acid solutions3-deoxyD-Glucoselao1-deoxy, 3-deoxy, & 4-deoxyD-Fructoseouon10

3/2/14& 10& D-Glucose 3-deoxy-glucosulose C H OH HO H H OH H OH CH2OH H O C OH HO H H OH H OH CH2OH H OH C OH H H OH H OH CH2OH H O C O H H OH H OH CH2OH H O elimination -2H2O CH2 O C H HO O HMF H CH2OH O HO H H OH H OH CH2OH HC OH HO H H OH H OH CH2OH CH2OH OH HO H OH H OH CH2OH OH OR CH2OH OH HO H OH H OH CH2OH CH2OH O HO H H OH CH2OH CH2 OH O H OH H OH CH2OH OR 1,2 enediol 2,3 enediol 2,3 enediol elimination -H2O D-Fructose CH2OH O HO H H OH CH2OH CH2 OH O H OH H OH CH2OH CH3 O O H OH H OH CH2OH CH2OH O O H H OH CH2OH H O CH2OH OC O OH OC H3C O O OH CH3 -2H2O -2H2O 1-deoxy-2-3-diketose 4-deoxy-2-3-diketose D-Glucose 3-deoxy D-Fructose 1-deoxy, 3-deoxy, & 4-deoxy In acid solutions