(12) Ulllted States Patent
`Fosdick et al.
`
`(10) Patent No.:
`(45) Date of Patent:
`
`US 8,361,235 B2
`Jan. 29, 2013
`
`US00836l235B2
`
`(75)
`
`(54) LOW-VISCOSITY REDUCED-SUGAR SYRUP,
`METHODS OF MAKING, AND
`APPLICATIONS THEREOF
`_
`.
`.
`Inventors. Lawrence E. Fosdlck, Troy, MI (US),
`Scott Helstad’ Dayton) OH (US);
`Yauching W. Jasinski, Dayton, OH
`(US); Guo-hua Zheng, Centerville, OH
`(US)
`(73) Assignee: Cargill, Incorporated, Wayzata, MN
`(US)
`Subject to any disclaimer, the term ofthis
`patent is extended or adjusted under 35
`U~3-C- 1540’) by 0 da>’S-
`12/991,868
`May 11’ 2009
`
`( * ) Notice:
`
`(21) App1.No.:
`(22) PCT Filed:
`NO.Z
`
`(51)
`
`(56)
`
`W0
`
`Int. Cl.
`(2006.01)
`6733 10/00
`(52) U.S. Cl.
`....................................................... .. 127/30
`
`(58) Field of Classification Search ............... ..
`None
`.
`.
`.
`See application file for complete search history.
`_
`References Clted
`U S PATENT DOCUMENTS
`4‘445‘933 A
`5/1984 Verwaerde et al.
`4,941,990 A
`7/1990 McLaughlip
`5,087,461 A
`2/1992 Levine eta.
`11%? A 3% IB°51k:’tV'° 6‘ 3‘-
`53:48,] 2
`12/1998 Tnaigetal‘
`6,068,705 A
`5/2000 Tang et al.
`............... .. 435/99
`al.
`,
`N
`§j§§§,§§3 3i
`353$ A§£‘1§‘33§§.eh et al.
`2006/0108081 Al
`5/2006 0 '
`t
`l.
`FOREIGN PATENTmlg(e)CaUMENTS
`WO2005/000905 A1
`1/2005
`
`*
`
`§ 371 (0)0):
`(2), (4) Date:
`
`Nov. 9, 2010
`
`PCT Pub. No.: W02009/137839
`PCT Pub. Date: Nov. 12, 2009
`
`* cited by examiner
`
`Primal? Examiner * Melvin C Mayes
`Assistant Examiner — Stefanie Cohen
`
`Prior Publication Data
`
`(57)
`
`ABSTRACT
`
`US 201 1/0061645 A1
`
`Mar, 17, 2011
`
`Related U.S. Application Data
`Provisional application No. 61/ 127,023, filed on May
`9, 2008.
`
`The invention provides a low~viscosity reduced—sugar syrup,
`methods of making such a 1ow—viscosity reduced-sugar
`Syrup’ and uses of Such
`
`17 Claims, 4 Drawing Sheets
`
`(87)
`
`(65)
`
`(60)
`
` E Exp9E
`
`E EXDIZ
`
`E Exp1oFE Exp1OD
`
`E Exp11B
`
`E Exp11A
`
`43DECSU
`«e
`
`
`e 36DE csu zsoecsu
`
`
`
`28DE csu
`
`TATE & LYLE AMERICAS LLC
`33
`28
`23
`18
`
`DE values EXHIBIT 1001
`
`=
`>'<G1‘ a--
`E E’
`en 3
`E 3101-!
`*3 a
`92
`.3
`5:9 ”
`O
`
`

`
`WWWMMWMWWWWWMWW
`
`US00836l235B2
`
`(12) Ulllted States Patent
`Fosdick et al.
`
`(10) Patent N0.:
`(45) Date of Patent:
`
`US 8,361,235 B2
`Jan. 29, 2013
`
`(54) LOW—VISC()SITY REDUCED-SUGAR SYRUP,
`
`(51)
`
`Int. Cl.
`
`(75)
`
`ME'I‘II()DS OF MAKING, AND
`APPLICATIONS THEREOF
`inventors: Lawrence E. Fosdick, Troy. Ml (US);
`Scott Hemad1 Dayton’ OH (US);
`Yauching W. Jasinski, Dayton, OH
`(US); Guo-hua Zheng, Centerville, OH
`US
`(
`)
`(73) Assignee: Cargill, Incorporated, Wayzata, MN
`(US)
`
`( * ) Notice:
`
`<2» Am No:
`(22)
`PCT Filed:
`
`Subject to any disclaimer, the term ofthis
`patent is extended or adjusted under 35
`Lmcmmwww.
`12/991,868
`May 11’ 2009
`
`(56)
`
`(2006.01)
`CI3B 10/00
`(52) U.S. Cl.
`....................................................... .. 127/30
`(58)
`gield 0fl.Cla.sSifific1afif0n _Searc1ht3":""
`None
`ee app ication
`e or comp e L seam its ory.
`_
`Referenws Cited
`U.S. PATENT DOCUMENTS
`4445933 A
`5/19g4 ve,-wael-de et a1,
`4,941,990 A
`7/1990 McLaughlin
`5,087,461 A
`2/1992 Levine et al.
`2
`%30Slk:>tViC 8181-
`=
`*
`“g e
`age: aaéana
`2:§§§:§§S 31*
`338% §E2’S333§;2i; eta"."""""""" “W”
`2006/0108081 Al
`5/2006 Onlc et al.
`FOREIGN PATENT DOCUMENTS
`
`(86)
`
`PCT N0.:
`
`PCT/US2009/043488
`
`W0
`
`WO2005/000905 Al
`
`1/2005
`
`§ 371 (°)(1)*
`(2), (4) Date:
`
`Nov. 9, 2010
`
`PCT Pub‘ No: V‘/02009/137839
`PCT pub. Date: Nov. 12, 2009
`
`* cited by examiner
`
`Primary Examiner —»—» Melvin C Mayes
`Ass1stanzExa/zzzner —— Stefanie Cohen
`
`Prior Publication Data
`
`(57)
`
`ABSTRACT
`
`US 201 l/0061645 Al
`
`Mar. 17, 201 l
`
`Related U.S. Application Data
`Provisional application No. 61/127,023, filed on May
`9, 2008.
`
`The invention provides a low-viscosity reduced-sugar syrup.
`methods of making such a low-viscosity reduced-sugar
`Syrup) and uses Ofsuch syrup
`
`17 Claims, 4 Drawing Sheets
`
`(87)
`
`(65)
`
`(60)
`
` Oligosaccharide
`Index-ll
`
`(DP3~14/DP15+) 1-4 0
`
`E Exp9E
`
`E Exp10F E Exp1OD
`
`E Exp12
`
`E Exp11B
`
`H Exp11A
`
`43DECSU
`
`
` ® 36DE CSU
`
`28DE CSU
`
`
` 2505 csu
`
` "
`
`33
`38
`—-w--vv-vv-—---~—-‘T wwvw% y«»4rvq—<qz—_:
`DE values
`
`43
`
`

`
`U.S. Patent
`
`Jan. 29, 2013
`
`Sheet 1 of4
`
`US 8,361,235 B2
`
`O)(Q.0.0Qt...TIIJI?1JII
`
`I311’
`
`01PQ
`
`J.ILI)I
`
`FIGURE 1
`
`IP15+
`
`DP6
`
`DP5
`
`DP3
`
`DP2
`
`D94
`
`UP?
`
`‘EffiéP D DPS
`
`Dextrose
`
`0 Oil
`
`20.38
`
`68.50
`
`60.00
`
`80.00
`
`’lO= .00
`
`120.013 l
`
`
`
`--I
`H
`3CD.422
`».F3‘co:3 C)
`4:. _. E; r;
`NJ(.71C)
`
`lg55 586
`
`
`mm
`
`DP’!.’5+
`
`DP‘!-1
`
`DP I3
`DP12
`
`DP‘! '2
`
`
`
`1
`
`'—(
`1:. ~I c-:(_lL1
`
`so 033
`K)‘:ya (x: L:
`0”!-4 Ln .4 «J
`
`U‘U 5
`
`are
`C’) ‘U:1:
`U '0 ‘xi
`
`I H
`
`E E
`
`
`
`
`
`
`IEEEII
`
`

`
`U.S. Patent
`
`Jan. 29, 2013
`
`Sheet 2 of4
`
`US 8,361,235 B2
`
`FIGURE 2
`
`
`
`100000000fi
`0 SDE MD
`.
`.
`.
`<> commercially avanlable maltodextrm (MD)
`6 commercially available syrups(CSU)
`ow-viscosity re -' uce a —sugar syrup
`
`10000000 ~l—~
`
`ml
`
`,
`
`»'''N
`01
`n.
`.3
`>-
`3:Sn
`
`8.1’
`>
`
`1000000 L
`
`~—-——~————-——~—~———~—--————-——~«—--~«-
`
`9 15DE MD
`
`100000
`
`12
`
`E
`
`Xp
`
`.
`
`.
`
`,5 .l .. -.. ._
`
`Exp11B
`
`10000
`
`
`
`EXP10F
`
`
`Exp11A
`
`Exp 10D
`
`1000 ~
`
`~-~-~
`
`- -
`
`--
`
`W...
`
`4DEC5U
`
` '”T T"fi*T“7”*T—7"“V*W l
`0
`2
`4
`6
`8 101214161820Z22426283032343638
`
`total of mono-and disaccharides (%)
`
`

`
`U.S. Patent
`
`Jan. 29, 2013
`
`Sheet 3 of4
`
`US 8,361,235 B2
`
`FIGURE 3
`
`23¢ Q"
`
`
`
`._......‘-”f.If'"__ .W;"IjLTf_L".:.;”If.:':Z_:T:_"'"““:”__::TII”“""”".--m____W.'"""
`
`9E
`
`E
`
`“P
`
`E
`Exp 10F
`
`
`
`Exp10D
`
`
`
`Exp11A
`
`_.
`
`3% Exp12
`
`~
`
`.
`.-
`
`%:
`
`43DECSU
`
`‘tgoiwxo
`
`
`
`
`® 36DE csu
`
`
`
`
`
`('5
`
`T:
`3
`
`Eo
`
`5
`g_
`9.
`53.
`'2
`9.
`Z
`Q;
`‘U
`E
`
`

`
`U.S. Patent
`
`Jan. 29, 2013
`
`Sheet 4 of4
`
`US 8,361,235 B2
`
`FIGURE 4
`
`
`WWWWWWW...
`105"‘"Wm"""m"'W""”"'"'""
`3 Exp9E
`
`:”W”"”""”""”' “mm”
`
`E Explorfi Exp1OD
`
`E A
`'2 3%
`—
`g E
`E 310
`3 2
`§ :3
`
`o
`
`a
`
`E
`
`113
`
`E Exp11A
`X”
`~~~~~~~~»--~—~---—-—---------~«----~~~~~—w-««—--~~~~~~~—-~-»-
`
`43DECSU
`
`
`
`305“)
`
`1 W
`
`my»-~
`
`r'"“
`
`18
`
`23
`
`22
`
`33
`
`33
`
`43
`
`L_“_mW___~~
`
`WDE values
`
`W W_
`
`__
`
`

`
`US 8,361,235 B2
`
`1
`LOW—VISCOSITY REDUCED-SUGAR SYRUP,
`METHODS OF MAKING, AND
`APPLICATIONS THEREOF
`
`CROSS REFERENCE TO RELATED
`APPLICATIONS
`
`This application claims the benefit of International Appli-
`cation No. P(“'l"/US2009/043488, filed 1 1 May 2009 entitled
`LOW-VISCOSITY REDUCED-SUGAR SYRUP, METH-
`ODS OF MAKING, AND APPLICATIONS THEREOF,
`which claims the benefit ofU.S. Application Ser. No. 61/127,
`023,
`filed 9 May 2008 entitled LOW VISCOSITY
`REDUCED SUGAR SYRUP AND METHODS OF MAK-
`ING. which are hereby incorporated by reference in their
`entirety.
`
`FIELD
`
`This invention relates to syrup, and more particularly to
`low—viscosity reduced-sugar syrup, methods of making such
`syrup, and uses of such syrup.
`
`BACKGROUND
`
`Syrups are produced from starch, which is liquefied in the
`presence of acid or enzymes or both to convert the starch to
`smaller carbohydrate chains. The particular carbohydrate
`composition o f the syrup is determined by the starting mate-
`rial as well as the acid and/or enzyme used, the temperature
`and pH at which the starch is liquefied, and the length of time
`the starch is exposed to the acid and/or enzyme. For example,
`the conversion of starch can be halted at an early stage result-
`ing predominantly in polysaccharides, which generally pro-
`duce low-to-medium sweetness syrups, or the conversion can
`be allowed to proceed until the carbohydrates are nearly all
`dextrose, which generally produce sweet syrups.
`Syrups are widely used in the manufacture of foods and
`beverages. In many cases, it is the individual saccharides or
`groups of saccharides (in other words, the carbohydrate com-
`position) that detennine syrup characteristics. High conver-
`sion starch syrups with more than 25% total mono— and di-
`saccharides and/or typically a dextrose equivalence (DE) of
`over 40 are used in various food products as sweeteners, for
`example, whereas low conversion starch syrups with less than
`25% total n1ono- and di—saccharides and/or typically less than
`DE of 40 have wide applications owing to their many useful
`characteristics. such as low sweetness, high viscosity, supe-
`rior water retention, heat stability, and chemical stability.
`These physiochemical properties are of particular importance
`to food manufacturing practices. Properties, such as appear-
`ance, texture. and mouthfeel of finished foods and beverages,
`are also often affected by the syrup used. There remains a
`need in the industry to provide syrup with minimal sugar,
`minimal sweetness, neutral taste, and viscosity low enough to
`allow for the easy handling ofsuch syrup.
`
`SUMMARY
`
`invention is directed to a low—viscosity
`The present
`reduced-sugar syrup, In one embodiment,
`the syrup has
`reduced sugar and low viscosity, with a DE of 20 to 52 or 26
`to 52. The reduced sugar has less than 25% total mono— and
`di—saccharides. or 0.5% to 25% total mono— and di—saccha-
`
`rides, and the viscosity is significantly lower compared to a
`starch-derived product that has a similar dry weight percent-
`age of total mono— and di—saccharides.
`
`10
`
`to ‘J:
`
`30
`
`35
`
`40
`
`45
`
`50
`
`55
`
`60
`
`2
`In a second embodiment, the low-viscosity reduced-sugar
`syrup with total mono— and di—saccharides of 25% has a
`viscosity not greater than 100,000 cPs at a temperature of
`100° F. and 78% DS. In another aspect, the total rnono- and
`di—saccharides is from 10% to 25% on a dry weight basis and
`the viscosity is not greater than 30,000 cPs at a temperature of
`100° F. and 78% DS. In yet another aspect, the total mono—
`and di—saccharides is from 20% to 25% on a dry weight basis
`and the viscosity is not greater than 15,000 cPs at a tempera-
`ture of 100° F. and 78% DS. In still another aspect, the total
`mono— and di—saccharides is from 0.5% to 10% on a dry
`weight basis and the viscosity is not greater than 250,000 cPs
`at a temperature of 100° F. and 78% DS.
`In a third embodiment, the low-viscosity reduced-sugar
`syrup has significantly lower levels of total mono— and di-
`saccharides (DPl+2) of less than 25% of the total carbohy-
`drates, significantly higher levels of oligosaccharides (DP3-
`I4) of greater than 60% of the total carbohydrates, and
`significantly lower levels ofthe polysaccharides (DP15+) of
`less than 15% of the total carbohydrates compared to a con-
`ventional starch-derived product that has a similar percentage
`oftotal mono— and di—saccharides on a dry weight basis.
`In a fourth embodiment, the low—viscosity reduced-sugar
`syrup has significantly lower levels of total mono— and di-
`saccharides (DPl+2) of less than 25% of the total carbohy-
`drates, significantly higher levels of oligosaccharides (DP3-
`10) of greater than 60% of the total carbohydrates, and
`significantly lower levels of the polysaccharides (DP15+) of
`less than 20% of the total carbohydrates compared to a con-
`ventional starch-derived product that has a similar percentage
`of total mono- and di—saccharides on a dry weight basis.
`In a fifth embodiment of the present invention, the low-
`viscosity reduced-sugar syrup has a DE offrom 20 to 52, or a
`DE of from 26 to 52, and a First Oligosaccharide Index of
`greater than 2.0. The low-viscosity reduced sugar syrup also
`in a sixth embodiment has a DE of from 20 to 52, or a DE of
`from 26 to 52, and a Second Oligosaccharide Index of greater
`than 3.0.
`
`In a seventh embodiment of the present invention, the
`low-viscosity reduced-sugar syrup has a less than 25% total
`mono— and di—saccharides, or 0.5% to 25% total mono— and
`di—saccharides, and a First Oligosaccharide Index of greater
`than 2.0. The low—viscosity reduced sugar syrup also in
`another embodiment has less than 25% total mono— and di-
`saccharides, or 0.5% to 25% total mono- and di—saccharides.
`and a Second Oligosaccharide Index of greater than 3.0.
`The details of one or more embodiments of the invention
`are set forth in the accompanying drawings and the descrip-
`tion below. Other features. objects, and advantages of the
`invention will be apparent from the drawings and detailed
`description, and from the claims.
`
`BRIEF DESCRIPTION OF THE DRAWINGS
`
`FIG. 1 is a chromatograph showing the DP composition of
`the low—viscosity reduced-sugar syrup in Example 1.
`FIG. 2 is a graph of the data of certain syrup samples of the
`present invention and conventional starch—derived products in
`Examples 4, 9, 10, 11, and 12.
`FIG. 3 is a graph ofthe data of certain syrup samples of the
`present invention and conventional starch—derived products in
`Examples 9, I0, 11, and 12.
`FIG. 4 is a graph ofthe data ofcertain syrup samples ofthe
`present invention and conventional starch—derived products in
`Examples 9, 10, 11, 12.
`
`

`
`US 8,361,235 B2
`
`4
`
`3
`IIDIZTAILED DESCRIPTION
`
`Terms and Definitions
`
`saccharides (DPl+2):3. As used herein with DE, “similar”
`refers to a conventional starch-derived product of DE:3.
`The term, “smooth mouthfeel”, as used herein. refers to a
`light and creamy consistency on the tongue and in the mouth
`as compared to more viscous syrup.
`The term, “starch-derived product”, as used herein. refers
`to a product obtained from the hydrolysis of starch.
`The term “sugar”, as used herein, refers to a nutritive car-
`bohydrate sweetener consisting of either mono- and/or di-
`saccharides.
`
`The tenn, “syrup”, as used herein, refers to aqueous solu-
`tions of sugars or starch hydrolysates.
`The term, “viscosity”, as used herein, refers to the resis-
`tance ofa fluid to flow. The viscosity ofa syrup is typically
`aifected by temperature and solid concentration. Viscosity is
`expressed in terms ofcentipoise (CP) at a given temperature
`and a given % DS. Brookfield viscometer (model LVDV-E
`I15, Brookfield Engineering Inc., Middlesboro, Mass.) with
`a l2-ml small sample adapter was employed for the determi-
`nation of viscosity. Temperature of the small sample adapter
`was controlled using a circulation water bath. Spindle #S-25
`was used while rotation speed was varied so that the percent
`torque fell between 25% to 75% during the viscosity mea-
`surements.
`
`The Syrup
`The chemical. physical, and functional properties ofsweet-
`eners vary according to their carbohydrate compositions. In
`order to understand the functional and nutritional properties
`of syrups, the actual carbohydrate composition (or “DP-N”)
`is most useful, though historically DE is also used. Syrups
`used to be classified into four types on the basis ofDE: type I
`having a DE ofabout 20 to 38; type II having a DE of38 to 58'.
`type III having a DE of 58 to 73 and type IV having a DB of
`73 and above. With respect to the carbohydrate composition
`of syrups, the sweetener industry produces starch-derived
`products typically containing 15% to 99% total mono- and
`di-saccharides (DPl+2), with the most widely used syrups
`containing more than 25% total mono- and di—saccharides.
`Generally, syrups having less than 25% total mono-plus di-
`saccharides are not very sweet and are extremely viscous and
`thick, making it a processing challenge to use such syrups due
`to, for example, high resistance to pumping, high resistance to
`flow, high adhesiveness to processing equipment, and being
`prone to microbial contamination. On the other hand, syrups
`with low viscosities, typically containing more than 25% total
`mono- and di-saccharides, do not have the processing chal-
`lenges compared to syrups with less than 25% total mono-
`and di-saccharides, but they impart sweetness and added
`sugar levels to foodstuffs where sweetness and/or added
`sugar levels may not be desired. Thus, there is still a need to
`provide a syrup with low viscosity for ease of use and at the
`same time with reduced total mono- and di—saccharide levels
`for use in food, beverage, and pharmaceutical products where
`sweetness and]or added sugar levels are not desired, but rather
`a neutral taste or minimal sweetness is desired.
`Food and beverage manufacturers continually seek new
`product and flavor opportunities to extend their existing prod-
`uct lines. develop new products. or reduce certain nutritional
`aspects of conventional products, such as reduced sugar.
`Reduced—sugar, neutral-tasting syrups or syrups with mini-
`mal sweetness having binding, bodying, bulking, coating,
`and water retention characteristics would allow food and
`beverage manufacturers to develop products not possible
`with today's conventional syrups or maltodextrins, such as
`developing savory products (i.e., products that not sweet but
`are piquant, pungent, or salty to the taste). The inventors ofthe
`present
`invention have surprisingly found low-viscosity
`
`Unless otherwise defined, all technical and scientific terms
`used herein have the same meaning as commonly understood
`by one of ordinary skill in the art to which this invention
`belongs.
`The term, “bodying”, as used herein, refers to additives
`used to impart desirable body, viscosity and consistency to
`foods.
`The term. “dextrose equivalent (DE)”. as used herein,
`refers to the degree of starch hydrolysis, specifically,
`the
`reducing value ofa starch hydrolysate material compared to
`the reducing value of an equal weight of dextrose, expressed
`as percent, dry basis, as measured by the Lane and Eynon
`method described in Standard Analytical Method E-26, Corn
`Refiners Association, 6”’ Edition, 1977, E‘,-26, pp. 1-3.
`The term, “DP-N”, as used herein, refers to the degree of
`polymerization, where N is the number of monomeric units
`(i.e., glucose or dextrose units) in the saccharide, thus DP-N
`reflects the composition of the carbohydrate. For example,
`DPI is a monosaccharide; DP2 is a disaccharide; DP1+2 is
`the total ofmono- and di-saccharides; DP3-l0 is the total of
`DP 3 to DPl(); DP] 1+ is the total of saccharides DPll and
`greater. The ratio of DP3 to DPIO divided by DPll+ is
`referred to as l"irst Oligosaccharide Index. and the ratio of
`DP3 to DPI4 divided by DPl5+ is referred to as Second
`Oligosaccharide Index. DP-N is expressed as a weight per-
`cent of an individual saccharide on a total carbohydrate dry .
`weight basis. It is noted that. typically, sweetness ofa syrup
`decreases as l)P increases and vice versa. Also. typically,
`viscosity ofa syrup increases as DP increases and vice versa.
`The DP-N composition ofa starch-derived product was deter-
`mined using high performance liquid chromatography
`(HPI_,C). A sample of low-viscosity reduced—sugar syrup was
`diluted with deionized water to 5% to 10% DS, de—ashed with
`ion exchange resins (Dowex 66 and Dowex 88, Dow Chemi-
`cal Co., Midland, Mich.)_, and filtered through a 0.45 micron
`filter before injection into the HPLC for DP carbohydrate
`analysis. DP separation was accomplished using two BioRad
`Aminex HPX-42A, 300 mm><7.8 n1in columns (BioRad, Her-
`cules, Calif.) in series using water as the eluent at a flow rate
`of0.20 ml/min at 65° C. Separated DP was quantitated with a
`refractive index detector
`
`us
`
`10
`
`20
`
`L; U.
`
`40
`
`45
`
`The term, “DS”, as used herein, refers to the percent dry
`solids as determined using the computer program, Refractive
`Index Dry Substance (RI-DS), Standard Analytical Method
`E-54, Corn Refiners Association, 6”‘ Edition, 1977, E-54, pp.
`1-1 I.
`
`The term, “oligosaccharide” as used herein, refers to a
`starch-derived product with a DP of from at least 3 to at the
`most 14. For example, DP3-7 is an oligosaccharide, DP3-l0
`is an oligosaccharide; DP3-14 is an oligosaccharide; DP4-6 is
`an oligosaccharide.
`The term. “polysaccharide”, as used herein, refers to a
`starch-derived product with a DP of at least 15. For example,
`DPI 5+ is a polysaccharide.
`The term, “short texture”, as used herein, refers to the
`cohesiveness of a starch-derived product when it is pulled
`apart and how elongated or stringy the binding material is, A
`starch-derived product having a short texture will not have a
`lot of elasticity when pulled apart, but will have small
`“strings” and/or short peaks when pulled apart and may return
`to its shape.
`The term, “similar”, as used herein with DP-N, refers to a
`conventional starch-derived product of total mono- and di-
`
`50
`
`Ux vi
`
`60
`
`

`
`5
`
`6
`
`US 8,361,235 B2
`
`tasting with binding,
`is neutral
`reduced-sugar syrup that
`bodying, bulking, coating, and water retention characteris-
`tics. This low-viscosity reduced-sugar syrup of the present
`invention addresses the unmet need across a range of product
`categories, including savory bars, clusters, sauces and glazes.
`In addition, using low viscosity reduced-sugar syrup of the
`present invention also allows food and beverage manufactur-
`ers to replicate original flavors due to neutral taste and/or
`minimal sweetness, but with less sugar and without the need
`to mask unwanted flavors. Also. surprisingly. the syrup can
`also be used as a liquid bulking agent and/or vehicle for high
`potency sweeteners due to its low viscosity and its minimal
`sweetness or neutral taste, and its ease to use in many pro-
`duction processes such as piping and spraying. Conventional
`starch-derived products such as maltodextrins and low DE
`syrups lack these advantages.
`The present invention relates to a low-viscosity reduced-
`sugar syrup. In one embodiment, the syrup has reduced sugar
`and low viscosity. with a DB ofabout 20 to about 52 or about
`26 to about 52. The reduced sugar has less than about 25%
`total mono- and di-saccharides or about 0.5% to about 25%
`
`total mono- and di-saccharides, and the viscosity is signifi-
`cantly lower compared to a starch-derived product that has a
`similar dry weight percentage of total mono- and di-saccha-
`rides. The viscosity in one aspect of the present invention is
`lower, from about 10% to about 99%, compared to the vis-
`cosity of a starch-derived product
`that has a similar dry
`weight percentage of total mono- and di-saccharides. The
`viscosity in a second aspect of the present invention is lower,
`from about 30% to about 95%, compared to the viscosity ofa
`starch—derived product that has a similar dry weight percent-
`age oftotal mono- and di-saccharides. In another aspect ofthe
`present invention, the viscosity of the low-viscosity reduced-
`sugar syrup is lower, from about 60% to about 95%. coin-
`pared to the viscosity ofa starch-derived product that has a
`similar dry weight percentage of total mono- and di-saccha-
`rides. In yet another aspect of the present invention, the vis-
`cosity ofthe low-viscosity reduced-sugar syrup is lower. from
`about 40% to about 75%. compared to the viscosity of a
`starch—derived product that has a similar dry weight percent-
`age of total mono- and di-saccharides.
`The viscosity of the low-viscosity, reduced-sugar syrup is
`lower when the viscosity is measured at a given DS and a
`given temperature as compared to a starch-derived product
`that has a similar dry weight percentage of total mono- and
`di-saccharides. In another embodiment of the present inven-
`tion, the Iow—viscosity reduced-sugar syrup with total mono-
`and di-saccharides of about 25% has a viscosity not greater
`than about 100000 cPs at a temperature of about 100° F. and
`about 78% DS. In a second aspect ofthe present invention, the
`low-viscosity reduced-sugar syrup with total mono- and di-
`saccharides of from about 20% to about 25% has a viscosity
`no greater than about 15,000 CPS at a temperature of about
`100° F. and about 78% DS. In another aspect of the present
`invention, the low-viscosity reduced-sugar syrup with total
`rnono— and di-saccharides of from about 10% to about 20%
`
`has a viscosity no greater than about 30,000 cPs at a tempera-
`ture of about 100° F. and about 78% DS. In yet another aspect
`of the present
`invention, the low-viscosity reduced-sugar
`syrup with total mono- and di-saccharides of from about 0.5%
`to about 10% has a viscosity no greater than about 250,000
`cPs at a temperature ofabout 100° F. and about 78% DS.
`The low-viscosity reduced-sugar syrup surprisingly has a
`very different carbohydrate composition from conventional
`starch-derived products that have a similar percentage oftotal
`mono- and di-saccharides on a dry weight basis. In one
`embodiment. the low-viscosity reduced-sugar syrup has sig-
`
`nifrcantly lower levels of total mono- and di-saccharides
`(DP1+2) of less than about 25% of the total carbohydrates,
`significantly higher levels of oligosaccharides (DP3—l4) of
`greater than about 60% of the total carbohydrates, and sig-
`nificantly lower levels ofthe polysaccharides (DP15+)ofless
`than about 15% of the total carbohydrates compared to a
`conventional starch-derived product that has a similar per-
`centage of total mono- and di-saccharides on a dry weight
`basis. In another embodiment, the low-viscosity reduced-
`sugar syrup has significantly lower levels oftotal mono- and
`di-saccharides (DP1+2) of less than about 25% ofthe total
`carbohydrates, significantly higher levels of oligosaccharides
`(DP3-10) of greater than about 60% of the total carbohy-
`drates, and significantly lower levels of the polysaccharides
`(DP15+) of less than about 20% of the total carbohydrates
`compared to a conventional starch-derived product that has a
`similar percentage oftotal mono- and di-saccharides on a dry
`weight basis.
`In still another embodiment of the present invention. the
`low-viscosity reduced-sugar syrup has a very different car-
`bohydrate composition compared to conventional starch-de-
`rived products having similar DE. In one aspect of the present
`invention, the low-viscosity reduced-sugar syrup has a DB of
`from about 20 to about 52 or from about 26 to about 52, and
`less than about 20% polysaccharides with DP1 1+ and thus a
`much higher First Oligosaccharide Index of greater than
`about 2.0 compared to a conventional starch-derived product
`having a similar DE. In another aspect of the present inven-
`tion, the low viscosity reduced-sugar syrup has a DB of from
`about 20 to about 52 or from about 26 to about 52, and less
`than about 15% polysaccharides with DP15+ and thus a much
`higher Second Oligosaccharide Index of greater than about
`3.0 compared to a conventional starch-derived product hav-
`ing a similar
`Methods of Preparing the Syrup
`The low-viscosity reduced-sugar syrup of the present
`invention can be made using methods that are routinely prac-
`ticed in the art. Syrups are produced from starch, which is
`liquefied in the presence of acids or enzymes or both to
`convert the starch to sugars. For example, an aqueous starch
`slurry containing about 35% to about 50% starch dry solid is
`acid-converted using about 0.015-0.025N hydrochloric acid
`at temperature range of about 250“ F. to about 320° F. for a
`given time length. Alternatively, the aqueous starch slurry is
`adjusted to a desired pH, then enzymatically converted with
`an alpha—arnylase at about 0.05-0.1% inclusion level at a
`temperature of about 180° F. to about 230° F. for a given time.
`The particular sugar composition of the syrup is determined
`by the starting material as well as the acid and/or enzyme
`used, the temperature and pH at which the starch is liquefied,
`and the length of time the starch is exposed to the acid and/or
`enzyme. For example, the conversion of starch to sugars can
`be altered at an early stage resulting in predominantly
`polysaccharides, which generally produces low-to-medium
`sweetness syrups and are very viscous, or the conversion can
`be allowed to proceed until the carbohydrates are nearly all
`dextrose, which generally produces very sweet syrups with
`very low viscosities. After liquefaction of starch into syrup,
`the syrup can be refined using filters, centrifuges, granular
`activated carbons or ion-exchange resins, and excess water
`can be removed.
`
`Generally, a starch stream is partially converted into syrup
`by acid-hydrolysis, typically under heat and pressure for
`varying amounts of time depending upon the desired proper-
`ties, or by enzyme-hydrolysis under controlled temperature
`and pH conditions for varying amounts of time depending
`upon the desired properties. The resulting syrup can be fil-
`
`I0
`
`15
`
`30
`
`40
`
`50
`
`55
`
`60
`
`65
`
`

`
`US 8,361,235 B2
`
`7
`tered or otherwise clarified to remove any objectionable fla-
`vor or color, and further refined and evaporated to reduce the
`amotuit of water. 1n the acid-enzyme process, starch is first
`partially hydrolyzed or liquefied by forming an aqueous sus-
`pension containing starch and incorporating therein an acid
`such as hydrochloric acid. The suspension is then heated to
`high temperatures to partially hydrolyze the starch. The sus-
`pension may be cooled and treated at a suitable concentration
`and pH range to enzymatically convert the partially hydro-
`lyzed starch. In the enzyme-enzyme conversion process. gen-
`erally, a starch slurry is formed and a starch liquefying
`enzyme is added and the starch slurry heated to partially
`hydrolyze the starch. The partial hydrolysis is usually carried
`out at a specilic temperature range. Any suitable starch liq-
`uefying enzyme may be used to partially hydrolyze the starch.
`The partially hydrolyzed starch slurry may then be treated to
`convert the starch.
`Starch can be obtained from a number of different sources
`using any number of methods routinely practiced in the art.
`For example. starch can be obtained from corn or another
`cereal feedstock such as rice, wheat, barley, oats. or sorghum
`through well known wet-milling and dry-milling techniques.
`In wet milling. corn or other feedstock can be steeped for a
`period of time and then ground to separate the germ, which
`contains the oil, from the other components. The remaining
`non-germ material is a slurry that includes starch, protein
`(e. g., gluten) and fiber, which can be separated into different
`streams. Starch steams also can be obtained from corn or
`
`another starch—rich feedstocks through dry milling tech-
`niques, which also are practiced routinely in the art. ln addi-
`tion, starch streams can be obtained from a root or tuber
`feedstock such as potato or cassava using either wet—n1illing
`or dry-milling processes.
`To produce the unique low-viscosity reduced-sugar syrup
`described herein, in one embodiment, a starch is made to a
`slurry of about 10% to about 70% DS and partially converted
`(either by acid- or enzyme-hydrolysis) to a starch liquor hav-
`ing a DB from about 1 to about 65, which is contacted with
`pullulanase enzyme, isoamylase enzyme, amylase enzyme,
`either alone or in combinations thereof. The inventors of the
`
`present invention have surprisingly found that a reduced-
`sugar syrup is produced to have an unexpected low viscosity
`when specific enzymes and their combinations are used to
`treat specifically chosen starch liquor under specific pH, tem-
`perature and time conditions.
`ln one aspect, from about
`0.001% to about 1.0% of such enzymes, alone or in combi-
`nation, is used based on the total dry weight ofthe starch. ln
`another aspect. from about 0.01% to about 0.8% of such
`enzymes is used.
`The unique syrup described herein is produced by hydro-
`lyzing the starch liquor in the presence of about 0.001% to
`about 1% ofamylase, isoamylase, pullulanase enzymes based
`on the total dry weight of the starch, alone or in combinations,
`at a pH of from about 3.0 to about 7.0 (e.g. pH about 3.0, pH
`about 3.5 to about 7.0, pH about 4.0 to about 7.0, pH about 4.5
`to about 7.0, pll about 5.0 to about 7.0, pH about 5.5 to about
`7.0, pH about 6.0 to about 7.0, pH about 6.5 to about 7.0, pH
`about 3.0 to about 6.5, pH about 3.0 to about 6.0, pH about 3 .0
`to about 5.5, plel about 3.0 to about 5.0, pH about 3.0 to about
`4.5, pH about 3.0 to about 3.5, or pH about 7.0) and a tem-
`perature ofabout 1 10° F. to about 160° F. (e.g., about 110° F.,
`about 115° 19.. about 120° F., about 125° F., about 130° F.,
`about 135° 17.. about 140° F., about 145° F., about 150° F.,
`about 155°
`or about 160° F.) for about 5 to 45 hours (e.g.,
`about 5 to 15 hours, about 15 to 25 hours, about 25 to 45
`hours, about 12 to 45 hours, about 12 to 40 hours, or about 25
`to 45 hours). It would be understood by those ofskill in the art
`
`8
`
`that the amount of both enzymes and the period of time of
`exposure to such enzymes (as well as the temperature at
`which such exposure takes place) can be adjusted accordingly
`so as to obtain a syrup having the DE and the accompanying
`DP profile and viscosity described herein. The amylase,
`isoamylase, and pullulanase enzymes can be obtained from
`commercial sources such as Sigma Chemical Co. (St. Louis,
`Mo.), Novozymes A/S (Krogshoejvej 36, 2880 Bagsvaerd,
`Denmark) Danisco A/S including Genencor (Langebrogade
`1, 1001 Copenhagen, Denmark), Enzyme Development Cor-
`poration (360 West 31” Street, Suite 1102, New York, N.Y.
`10001-2727), Vereniuin Corporation (Cambridge, Mass).
`Amano Enzymes lnc. (1-2-7, Nishiki, Naka-ku, Nagoya 460-
`8630 Japan), Hayashibara (1 -2-3 Shimoishii. Okayama 700-
`0907. Japan) or purified from natural or recombinant sources
`using known methods. lt is noted that with the new recombi-
`nant gene technologies. it is possible for new enzymes to be
`more effective at temperatures higher than about 160° F. ln
`contrast. at a temperature of about 1 10° F. to about 150° F.,
`low-temperature enzymes will be more effective.
`Properties and Applications ofthe Syrup
`The unique carbohydrate composition of the present inven-
`tion results in a low viscosity syrup, which allow