All

IDF Symposium “Lactose and its Derivatives”14-16 May 2007, Moscow, Russia

3A Business Consulting3A Business Consulting 11

May 15, 2007

Market developments and industry challenges for lactose and lactose

derivatives


3A Business model

Strategy and businessdevelopment for all elements of the food value chain

Key competenceswithin functional foods, health& wellness and ingredients

Core structure - global network


3A multi-client reports

3A Business Consulting

November 2005

Global Market Analysis of Whey and Lactose Products 2004-2009 - From commodities to value

added whey protein fractions and lactose derivatives

Dairy Ingredients in Nutritional Sectors Supply/Demand/Forecasts 2005-2010

USA, EUROPE

Date

GIRACT 3A BUSINESS CONSULTING

Website: www.giract.com

Email: [email protected]

Website: www.3abc.dk

Email: [email protected]

S H A I N W R I G H TCONSULTING AND RESEARCH GROUP PTY LTD

China – dairy opportunities unlimited

- dairy production, consumption & trade, trends, players and outlook 2008

3A Business Consulting

February 2006

Update version available from August 2007


Lactose- introduction

Lactose- marketoverview

Lactose- lactose

derivatives

Market developments and industry challenges for lactose and lactose derivatives

Lactose- summing

up


Global whey production figures - 2006

177

167

9,6

0 20 40 60 80 100 120 140 160 180 200

Total whey production

Global whey resultingfrom cheese

Global whey resultingfrom casein

million tonsSource: 3A Business Consulting

~ approx. 6%

~ approx. 94%

Liquid whey supply CAGR approx. 2-3%

2001-2006


Million tons / year

Total world production

177Industrially

utilized

124

Whey powder, lactose

70

WPC/WPI producing permeate

43

Feed, fertilizer,

waste

53 Demineralized, blends, etc.

11

177

World whey utilization - 2006

70%30%

Source: 3A Business Consulting

124


Whey and lactose product universe



CheesewheyCaseinwhey

LactosePermeatepowder

Lactose –pharma grade

Lactosederivatives

GalactoseLactuloseLactitolLactobionic acidGOSLactosucroseSialyllactoseTagatose

Applications:PharmaNutritionHealth careFoodFeed

Added value level

Lactose products universe

Whey raw

materialLactose IILactose I Lactose III



Value-adding in whey processing (illustration)

Value creation

Technology requirements

HighLow

Low

High

Whey protein fractionsBioactive peptides

WPI/WPH

WPC80WPC35

WP feedWhey powder


Permeate powder

LactitolLactulose GOS LBA

Lactosucrose

Sialyllactose

Lactose-pharma

Galactose

Lactose




Lactose- lactose

derivatives


Lactose- summing

up


Overview of global lactose production 2002-2006

EU 49%

US36%

NZ12%

ROW3%

EU 46%

US37%

NZ13%

ROW4%

Global production: 724,000 tons

Global production: 870,000 tons

2002 2006

The EU and the US are the major producing countries representing more than 83% of the global production (down from 85% in 2002)

New Zealand is the only other major producing country with 13% of the global production corresponding to 110,000 tons (up marginally from 12% in 2002)

Source: USDEC, University of Wisconsin, 3A Business Consulting

CAGR: approx. 5%


Commodities still make up the most significant part of the lactose business

68%

32%

High value-added lactose ingredients (lactose derivatives) US$ 217 million

Commodities (lactose, permeate powder) US$ 460 million


66%

34%

Commodities (lactose, permeate powder) US$ 1265 million

High value-added lactose ingredients (lactose derivatives) US$ 665 million

US$ 677 million US$ 1,930 million

Market value growth 185%

2004 2006


Cheese wheyCasein whey

LactosePermeatepowder

Lactose – pharma grade

Lactosederivatives

Applications:PharmaNutritionHealth careFoodFeed

Added-value level

Illustration of lactose ingredient producers

Whey raw

materialLactose IILactose I Lactose III

Numerous companies

Campina/DMVFriesland Foods DomoMeggleHilmar IngredientsFonterra

Friesland Foods DomoSolvayDaniscoADMFerro PfanstiehlPuracInalcoFresenius-KabiBiofac



World's leading lactose producers

Friesland Foods Domo8%

Leprino Foods6%

All others 50%

Arla Foods3%

Fonterra12%

Meggle 4%Lactalis

3%

Hilmar Ingredients

5%

Campina/DMV10%

In 2006, 7 out of the 8 biggest lactose producers in the world are found in the EU and the US

Fonterra has achieved the position as the world's biggest lactose producer with 12% market share


Carbery, Anchor AlcoholAlcohol

Purac, Cargill, Hendan Jindan, ADM, GalacticLactic acid

Solvay, Sandoz, US Dairy Ingredient CompanyLactobionic acid

Danisco, Purac, Towa, NikkenLactitol

Morinaga, Milei, Solvay, Inalco, Fresenius-Kabi, Relax, Biofac

Lactulose

Hayashibara, EnsuikoLactosucrose

Friesland Foods Domo, Morinaga, Snow Brand, Yakult, Nissin

GOS

ProducersProducts

Lactose/permeate derivatives and producers

Note: In 2006 Arla Foods Ingredients stopped their production of tagatose due to economics


Lactose segment break down – 2005

Source: 3A Business Consulting/EWPA/ZMP

EU production distribution/applications

Infant formula 18%

Bakery products 5%Pharmaceuticals

28%

Other processed food incl. meats

30%

All other uses3%

Chocolate confectionery

industry 16%

EU consumption approx. 325,000 MT; not same distribution/applications


Lactose segment break down –US market applications 2005

All other uses13%

Nutraceuticals, Pharmaceuticals

5%

Confectionery industry

16%Infant formula

66%

Source: 3A Business Consulting/ADPI

Total US consumption approx.

130,000 MT


Lactose price development from 2004 to date

0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

1

2004 2005 2006 2007

$/lb

Lactose prices

Growth: >300%

Source: University of Wisconsin, EWPA, Trade interviews

0

0,5

1

1,5

2

2,5

2004 2005 2006 2007

EUR/kg

Growth: >300%

US market

EU market


Top 10 lactose exporting countries 2005

0 50 100 150 200

Lithuania

Ireland

Denmark

France

Australia

Italy

New Zealand

Germany

Netherlands

US

1,000 MT

Growth since 2002

+ 54%

- 7%

+ 53%

+ 152%

+ 234%

- 13%

+ 93%

+ 15%

+ 23%

+ 9%

Source: FAOSTATS & 3A Business Consulting


Top 10 lactose importing countries 2005

0 20 40 60 80 100

Germany

United Kingdom

Korea

Spain

France

Vietnam

Mexico

Netherlands

China

Japan

1,000 MT

Growth since 2002

+ 188%

+ 160%

+ 31%

+ 189%

+ 15%

+ 28%

+ 0%

+ 22%

- 33%

+ 0%

Source: FAOSTATS & 3A Business Consulting




Lactose- lactose

derivatives


Lactose- summing

up


Permeatepowder

Lactose

Biogas

Nisin

Fertilizer

Animal feed

Lactulose

Effluent plant

GOS

LBA

Mineral powder

Beverages

Protein standardisation

Galactose/glucose syrup

Volume

Innovation and value added

Lactose derivatives –strategic mapping

Commodity Main stream Specialty

Alcohol

Lactic acid

Lactosucrose

Lactitol

Galactose

Sialyllactose


Market positioning/segments: Bulking agent for sugar free products, low sweetness, high viscosity and low hygroscopicity properties, non-cariogenic, reduced calorie-effect. Also some pharma use

Competing products: Food: maltitol, isomalt and erythritol. Possibly isomaltulose, trehalose and tagatose. Pharma: lactulose

Competition: Danisco (DK), Purac (NL), Towa (J), Nikken (J)

Market size: Approx. 10,000 MT and US$ 50 milllionCAGR: 2-4%

Market data - Lactitol

Overall evaluation/market potential/future prospects


New products with Lactitol

Total number of new products: 865

Source: Mintel, 2001-2007


Product examples with Lactitol

Nutrabien Chocolate Chip Cookie is sugar-free, low in sodium and high in fiber. The product is free from colorants and preservatives. Also available is an Oats variant.

Alimentos NutraBien –Nutrabien

Chocolate Chip CookieYakult – Yakult Bifiene

Fermented Drink

Yakult Bifiene is a milk-based fermented drink that contains bifidobacterium breve Yakult, which is said to help promote good intestinal function.

Source: Mintel


Market data - Galactooligosaccharides

Market positioning/segments: Prebiotic, non-cariogenic, positive effect on constipation. Main potential segments include beverages, dairy products, infant formula

Competing products: Other prebiotics/oligosaccharides

Competition: Friesland Foods Domo (NL), Morinaga (J), Snow Brand (J), Yakult (J), Nissin (J); possibly new players




New products with galactooligosaccharides




Product examples with galactooligosaccharides

Source: Mintel

Kasdorf – NutriciaBagó Nutrilon Premium – Infant Milk powder

Nutricia Bagó Nutrilon Premium Después de la Primera Infancia Infant Milk Powder is a modified milk powder, with prebiotics, made from partially skimmed milk, maltodextrin, vegetable oil, vitamins and minerals. It is said to help reinforce the immune system of infants.

Coca-Cola – Ooo –Muscat Au Lait

A milky drink with 1% muscat grape juice and oligosaccharide.


Market data - Lactulose

Market positioning/segments: Pharma: mainly treatment of constipation, Food: as a nutraceutical ingredient in infant formula, diabetic foods, soft drinks etc.

Competing products: Other oligosaccharides in food, lactitol in pharma

Competition: Morinaga (J), Solvay (B), Inalco (I), Fresenius-Kabi (AT), Relax (SA), Biofac (DK)




New products with Lactulose




Product examples with Lactulose

Lactulose are prune flavouredlaxatives which are said to relieve constipation. It is suitable for adults and children aged seven years and older.

Merck Génériques –Merck GénériquesLactulose – Prune

Flavoured Laxatives

Source: Mintel

Pasteur has launched Regular Motions Yogurt Drink, which contains synbiotics for regular motions, complex dietary fibre, complex oligosaccharides and prune juice.

Pasteur – Pasteur –Regular Motions

Yoghurt Drink


Lactose/permeate derivatives overview 2006

Market overview

870

300

35 21 100

100

200

300

400

500

600

700

800

900

1000

Lactose Permeatepowder

Lactulose GOS Lactitol

000´ tons

2-4% 10-20% 0-5% 10-20% 0-5%

Source: 3A Business ConsultingMarket growth rates




Lactose- lactose

derivatives


Lactose- summing

up


Expected market development for lactose



Growth opportunities ahead for lactose and derivatives for the industry 2006-2010

Marketgrowth

Value(US$/kg)

β

HighLow

Low

High


Sialyllactose

LBA

Lactosucrose

Lactose-pharma

GOS

Permeate powder

Lactose

Lactulose

Lactitol

Commodities

High-end derivatives

Emerging


Regulatory challenges for new dairy ingredients/lactose derivatives

Ingredient approval EU – Novel Foods regulation and the US –FDA Food additive petition/GRAS approval

Documentation of health benefits


A number of strategic alliances exist within dairy ingredient processing


Examples of strategic alliances within lactose processing

Lactose-pharma

LactuloseGOS


Whey ingredients set for growth

The market for industrially utilised whey ingredients will continue to grow particularly in food and nutrition applications

High-value added lactose ingredients will also see moderate growth rates due to increasing demand from the nutritional and pharmaceutical segments, however the pharma market face competition from other excipients e.g. MCC and starch

Lactose derivatives such as lactulose, lactitol alongside galactooligosaccharides are showing interesting new application opportunities and significant annual growth rates

New lactose derivatives such as LBA and sialyllactose are emerging and will develop into commercial products


Market dynamics for lactose

Global market demand for dairy products and dairy ingredients approx. 2.8% CAGR exceeds current global milk supply growth of less than 1%

The dramatic increase in the price of SMP due to lower production and elimination of EU and US stocks have had a knock-on effect on the price of WP and lactose

A growing demand for lactose for pharma and nutrition usage as well as for lactose derivatives and protein standardization of SMP has further pushed up lactose prices

High end applications for lactose will continue to be locked into lactose, whereas low end applications will try to reformulate product compositions

Increase in lactose supply will not likely keep up with demand

Dairy commodities/ingredients including lactose will remain highpriced well into 2008 and the foreseeable future


Thank you for your [email protected]


University of Alberta

Paul Jelen Dept. of Agricultural, Food and Nutritional

ScienceUniversity of Alberta

Edmonton, Alberta, Canada

Properties of lactose as determinants of crystallization behaviour and of

industrial applications

Lactose

Milk of (almost) all mammalsPrimary source of energy for the neonateHighest concentration (7%) in human milkPrincipal component of cow’s milk (4.5 - 5%; 53% of non-fat solids)Cheapest reducing CHO on the market

Concentration of lactose in milk of different mammals

Human

Cow

Buffalo

Goat

Sheep

7.1

4.6

4.8

4.3

4.8

H2O content (%)H2O content (%)SpeciesSpecies Lactose content (%)Lactose content (%)

87.1

87.3

82.8

86.7

82.0

Schematic representation of the lactose disaccharide molecule

Important basic properties of lactose

Disaccharide (glu-gal)Two stereoisomers (α- and β) > mutarotationReducing sugar >>> browning reactionLow sweetness (20% of sucrose at 5% conc.)Low solubility (18% w/w at 20°C)

> low osmotic pressure> slow crystallization

Forms of lactose

α - lactose, β – lactose In solution the ratio of α : β is about 1 : 2 Effect of temperature and mutarotation on

> solubility> sweetness> crystallization behaviour

In crystalline state> α – lactose contains one H2O molecule> α – lactose anhydride (heating above 130oC)> β – lactose (above 95oC) contains no H2O

Properties of lactose affecting the dairy industry

> Fermentable by lactic acid bacteria > Crystallizes in highly concentrated dairy foods

(sweetened condensed milk, ice cream, whey cheese mysost)

> Low sweetness – unsuitable as a sweetening agent, can be improved by hydrolysis

> Lactose malabsorption limits consumption of dairy foods by lactose intolerant consumers

> Fermentable by aquatic bacteria - high BOD of whey

> Unique crystallization behaviour

Focus of this presentation

Crystallization phenomena Model systems – experimental methodsSolubility Real life dairy foods

Sweetness phenomenasensory impact in dairy foodsuse for protein standardization

Lactose hydrolysisLactose derivatives and pharma-lactose

Centuries of dairy science:lactose

1633 – Bartoletto isolated and described lactose as “essential salt without nitrogen”

1688 - Ettmueller isolated lactose from whey and purified by recrystallization

1814 – 1820 analytical work by Berzelius 1902 – 1942 fundamental work by Hudson1936 – 2007 lifetime achievements of Prof.

Andrei Georgievich KHRAMTSOV

Lactose crystallization

Supersaturated solutionConcentrated dairy systems (condensed milk, ice-cream, whey cheese)Whey or whey permeate >> evaporation and cooling for production of lactose commodityCrystalline habit and crystal growth mechanism (α-lactose)

Single crystal method to study the crystallization phenomena

Method described by Professor J.A. Kucharenko from Polytechnical Institute, Kiev, for study of sucrose crystallization

Series of 12 articles published in “The Planter and Sugar Manufacturer” (New Orleans), from May 12 to July 28, 1928 (volumes 80 and 81)

Crystallization velocity, density, effects of impurities, solubility, supersaturation

Single crystal method adapted to study lactose crystallization

Lactose crystal growth: single crystal experiments

Van Kreveld (1966 – 1969): crystals grow from the apex of a pyramid down

Jelen (1971 – 74): effect of supersaturationand growth promotion by mineral impurities

Visser (1980 – 1983): crystal growth retarders, structure of lactose crystal

Jelen (1996) – crystallization velocity with assumption of bottom plane growth

Lactose solubility

Temperature oC Concentration of saturated solution (g / 100 g H2O)

___________________________________________

30 oC 24.050 oC 44.070 oC 77.8 80 oC 98.9

Effect of minerals on lactose solubility at 30oC

Salt added Estimated solubility(5 g / 100 g H2O) (g / 100 g H2O)

__________________________________________________

Control (no salt) 24.4Calcium chloride 24.3Magnesium sulphate 23.0 Lithium chloride 21.9Potassium phosphate 26.5

Lactose crystallization velocity

Average growth rates of lactose crystals in model lactose solutions with or without the addition of salts.

Lactose crystals under microscope

Scanning electron microscopy of spray dried demineralized permeate powder (courtesy Dr. Kalab, Ottawa).

Light microscopy of demineralizedwhey permeate powder (courtesy Dr. Kalab, Ottawa).

Growth rates of lactose crystals (30oC, supersaturation 9 g)

Exposed face

AllSidesTop (truncated)Bottom

Crystallization rate (mg m-2 min-1)

160.9 ± 12.12.5 ± 3.0

-0.6 ± 3.4211.8 ± 69.3

Growth rates of lactose crystals(30oC, supersaturation 10g)

Assumptions

Growth on all sides

Growth on bottom side only______________________________________Sucrose

Approximate Crystallization rate (mg m-2 min-1)

80 (Jelen 1972)

350 (Bhargava/Jelen, 1996)

320 (Smythe, 1971)

Promoters and inhibitors of crystal development

Promoters

Lithium chloride

Calcium chloride

(at low concentrations)

Some phosphates

Other electrolytes (?)

β-lactose

Riboflavin

Galactose

Gelatin

Potassium salts

Inhibitors

Lactose solubility and crystallization in whey, UF permeate or dairy foods

Nucleation vs crystal growthComponents affecting solubility and crystal

growth Very high supersaturation – nucleation

favored Ice cream, frozen desserts, Sw. Cond. MilkNorwegian whey cheese Mysost

Lactose crystals in whey cheese Mysost




Effect of mineral impurities on lactose crystals

Sweetness of lactose

Much lower than sucrose (20 % at 5% conc.)Effect of temperature and concentrationAddition of less that 1% lactose to milk

clearly noticeable (Jelen & Michel, 1999)Lactose used for down standardization of

protein in dry milkSweetness can be increased by hydrolysis

Lactose hydrolysis

Low solubility (sandiness)

Low sweetness

Lactose intolerance

Oligosaccharides

50 Mpersons market in USA alone

Acid + heat

Free enzyme

Immobilized enzyme

Disrupted bacteria

MethodsReasonsReasons

Characteristics of lactose hydrolysis methods

• Acid-catalysed hydrolysis – technological and material problems

• Immobilised enzyme technology– rarely succesful (Valio)

• Membrane - based enzyme reactors– theoretically interesting, rarely used

• Free (soluble) purified enzymes – used in industrial practice– Tetra-lacta process– home use in milk or as a dietary aid (pill)

How widespread is lactoseintolerance in the world?

Lactose hydrolysis by disrupted lactic acid bacteria

• framework: Canadian research network on lactic acid bacteria for applications in dairy industry (University of Alberta).

• objective: to investigate a “simple” approach to the lactose hydrolysis problem using lactase enzyme produced by common dairy bacteria after their disruption as crude enzyme extracts (CEE) obtained by microfluidization

Components of the proposed lactose hydrolysis process

well defined (GRAS) enzyme source (Lactobacillus bulgaricus 11842)

well defined (GRAS) medium (skim milk, whey)culture production, separation and disruption (bead

mill, high pressure homogenizer, Microfluidizer)use of the “dirty” CEE for lactose hydrolysis without

additional purification

Schematic representation of the proposed process

culture propagation (skim milk)

centrifugation or MF

culture disruption milk processing

(NF, HPUF, UF, DF)

viable cell deactivation (MF) lactate, salts

reprocessed milk

addition to milk or whey UF permeate

downstream processing

downstream processing

SEM images of Disrupted L. bulgaricus 11842

Control 1 pass (homogenizer)

Sonication (6 min) Bead Mill (6 min)

Lactose derivatives: GALACTO - OLIGOSACCHARIDES

Di-, tri-, tetra- or higher -saccharides

Intermediate sweetness

Highly heat and acid stable

Bifidogenic factor

Non-digestible

Probiotic foods

Nutraceutical (FOSHU) foods (anticarcinogenic)

Non-cariogenic foods

Competing against inulin

PropertiesProperties Applications

Lactose derivatives as value added products

Lactulose: 16 kt/yearLactitol: 10 kt/year in 1 plantLactobionic acid: potential for 1kt/year in 1

German plantOligosaccharides:

Galactooligosaccharides: n/aLactosucrose: 1.6 kt/year

Pharmaceutical lactose products

α-lactose:100 mesh (>125 µm)Agglomerated / granulatedSpray dried (80% crystals, 20% amorphous)

Anhydrous lactose:α -lactose (heated >130°C)β-lactose (crystallized >93°C)

Pharmaceutical lactose processes

Whey or UF permeate (crystallization)

Crude lactose

Refining recrystallization

Refined α-lactose

Heating >130°C

Anhydrous α -lactose

Spray drying

Spray dried α-lactose

Crystallization on roller driers >93 °C

β-lactose

Industrial processors of pharma-lactose

Manufacturer Product trade name

Lubricant

Meggle

BASF

DMV

TablettoseCellactose

Ludipress

Pharmatose

-Cellulose

PVP

Lactitol

New aspects of lactose science and industrial applications

Use of microcrystalline lactose as a flavourcarrierLactose effects in microencapsulation of fat by WPCCaking in bulk lactoseUse of lactose for protein standardization in non-fat-dry-milk and fluid milk

Traditional uses of isolated lactose

Food(1996 total 425 kt)

Infant foodsConfectioneryOther (bakery, dry mixes)Dairy (protein standardization)

Other(1996 total 175 kt)

PharmaceuticalsFermentationFeedsDerivatives

THANK YOU!


LACTOSE CRYSTALLIZATION

FROM SATURATED SOLUTIONS

Aram Galstyan

GNU All-Russia Dairy Research Institute, Moscow, RussiaDepartment of gerodietical and special products

Тел./Факс: +7 (495) 236-02-36www:vnimi.org

E-mail: [email protected]

Product qualitative index*

Consistence

HomogeneousNot less than 400.000 crystals in 1 mm3 of product

Crystals average size ≤ 10 µm

Technological operations

Crystallization FermentationGerms

Vacuum

Isohydric Lactose preparation

Immobilizing

Consumed

Small dispersionlactose (3-4 µm )

Powder Suspension

* Радаева И.А., Гордезиани В.С., Шулькина С.П. Технология молочных консервов и ЗЦМ: Справочник– М.:Агропромиздат, 1986.Чекулаева Л.В., Чекулаев Н.М Сгущенные молочные консервы. – М.: Легкая и пищевая пром-ть, 1982. Чекулаева Л.В., Полянский К.К., Голубева Л.В. Технология продуктов консервирования молока и молочного сырья.– Воронеж: Изд. ВГУ, 1996.

Introduction

Technological requirements

Crystallization

Saturation level

To control energy exchange processes

Prime material availability

To control mass distribution processes

Fermentation

To have a ferment

To know the activity, optimal conditions

To know the properties, decide the adding time

Introduction

Crystallization

Homogeneous Heterogeneous

Heterogeneous crystallization nucleus

Homogeneouscrystallization nucleus

The composition of exuded crystalsdoes not correspond to

composition of crystallization centers

The composition of exuded crystalscorresponds to

composition of crystallization centers

1) Shabalin V.N., Shatoxina S.N. Morphology of biological fluids. – M.:Chrizostom, 20012) Rosenberger F. Fundamentals of Crystal Growth.— Berlin, 19793) Ohtaki H. Crystalization Processes. – Wiley, 20014) Hartel R.W. Crystallization In Foods.- Kluwer Academic Publishers, 20015) Веригин А. Н., Щупляк И. А., Михалев М. Ф. Кристаллизация в дисперсных системах: Инж. мет. расчета.- Л.: Химия, 1986 6) Портнов В.Н., Чупрунов Е.В. Возникновение и рост кристаллов.-М.:Изд. Физ.-мат.лит., 2006

http://www.wikipedia.org http://www.xumuk.ru http://www.paceka.ru http://www.cheresources.com http://www.geo.web.ru и др.

Introduction

Condensed milk with sugar Boiled condensed milk with sugar

Raw materials acceptance, storage and preparation

Dry milk products reduction at

water temperature 40-60 °C Lactose fermentative hydrolyses (39-41 °C, for 3h)1

Dispergration of the fatty

component

Heating (75-77 °C)

Sugar dissolution

Heating and pasteurization

(90-95 °C for 2-3 min) Heating

Cooling (32-37 °C)

Crystallization 3

Homogenization

(15-16 Pa) at T ≥ 30 °C Heat treatment (cooking) (95 °C and more for 1-3 hours) 2

Cooling (20 ± 2 °C) Cooling to 80-85 °C and homogenization (15-16 MPa)

Packaging Packaging

Marking Marking

Storage and sale

1 Employed with a purpose of prevention the uncontrolled crystallization & speeding-up cooking time 2 Duration depends on the temperature & fermentation process 3 The adding of priming material in vacuum meant. In manufacture of sugar- containing condensed milk “cooking” is not employed.

Principle technological schemes of manufacture of sugar containing condensed milk products

Materials and Methods

Model product’s normalized indices

≤ 15Allowed size of lactose crystals, µm ,

≤ 3-615

Viscosity, Pa*сvalid within 2 monthsvalid within 2 to 12 months

≤ 45Acidity,0Т

≥ 28,5≥8,5

Total mass proportion of milk dry materials, %also fat, %

≥ 43,5Mass proportion of saccharose, %≤ 26,5Mass proportion of moisture, %

StandardsIndex appellation


Х51000,0Total productХ4255,0WaterХ3450,0Granulated sugar (dry materials proportion 99,8%)Х282,0Milk fat (fat proportion 99,8%)

Х1213,0Dry skimmed milk (dry materials proportion 95%, fat proportion 1,5%)

CodingRecipesComponents

Recipes of sugar-containing condensed milk productsand established conventional coding

Х5=Х4 + Х1 + Х2 + Х3

Y14StoringY7Cooling

Y13MarkingY6Pasteurization

Y12MixingY5Homogenization

Y11PackingY4Heating

Y10CookingY3Dispergration

Y9CrystallizationY2Germs bringing in

Y8VacuumingY1Dissolution

CodingAppellation ofthe operation

CodingAppellation ofthe operation


Y15 X5---ТО15

Y13 X5Y14X5Y14X5Y14X5ТО14

Y7 X5Y13X5Y13X5Y13X5ТО13

Y10 X5Y11 X5Y11 X5Y11 X5ТО12

Y11 X5Y9X4123Y9X4123Y9X4123ТО11

Y7X4123Y7X4123Y7X4123Y7X4123ТО10

Y8X4123← ZY8X4123← ZY8X4123Y8X4123ТО9

Y6X4123Y6X4123Y6X4123Y6X4123ТО8

Y1X3Y1X3Y1X3Y1X3ТО7

Y4X412Y4X412Y4X412← ZY4X412ТО6

Y5X412Y5X412Y5X412Y5X412ТО5




Y4X4Y4X4Y4X4Y4X4← ZТО1

C/CBА

Possible modification of germs adding timeOperationssequence

ТО – technological operation; Z – time point of bringing in of germs

Operative models: condensed milk with sugar (A,B,C) andcondensed milk with sugar “cooked” (С/)


12015 302

0 Time (Days)

9060 7545 105

Time point of sampling for microscoping

0 – end of technological process and beginning of analysis120 – end of analysis

Storage temperature

6-100C


14-15CaCO3Calcium carbonate3

not presentTiO2Titanium dioxide2

Not present

≥ 98

SiO2Silicon dioxide1

Solubility in water at рН≤7,0, mg/l

Properties, %

Molecular formula

Products№

2 60040175 00010

7 00030220 0009

21 00020270 0008

50 00015500 0007

98 00012770 0006

Lactose crystals likely amount in 1mm3 of

product, M

Crystals average size, µm

Lactose crystals likely amount in 1mm3 of

product, M

Crystals average size, µm

∑ ∑∆= )2/( 2nvnаUU – homogeneity coefficient; ∆а – crystal size limit, µm; n – crystals frequency; v – given and mean sizes divergence, µm

D – mean value of crystals size, µm ; n – crystals frequency; а – crystals linear size, µm

Coefficient of crystals homogeneity was calculated by the means of N. Figurovskii’s formula

Crystals average size was calculated by formula:

D = ∑na / ∑n


Distribution of samples with no crystallization effect when germ size is 3 µm and its corresponding dosage 0,02…0,10% of product mass

14%

16%

22%

31%

46%

0

10

20

30

40

50

60

700.10

0.09

0.080.05

0.02

Y14X5

Y13X5

Y11 X5

Y9X4123

Y7X4123

Y8X4123← Z

Y6X4123

Y1X3

Y4X412

Y5X412

Y3X2

Y4X41

Y1X1

Y4X4

Model C

Results

51%

68% 21%

28%

40%

0

10

20

30

40

50

60

700.10

0.09

0.080.05

0.02

Distribution of samples with no crystallization effect when germ size is 4 µm and its corresponding dosage 0,02…0,10% of product mass

Y14X5

Y13X5

Y11 X5

Y9X4123

Y7X4123

Y8X4123← Z

Y6X4123

Y1X3

Y4X412

Y5X412

Y3X2

Y4X41

Y1X1

Y4X4

Model C

Results

0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4C

oeff

icie

nt o

f hom

ogen

eity

, U

3 4

Germ size, µm

Silicon dioxideTitanium dioxideCalcium carbonate

Y14X5

Y13X5

Y11 X5

Y9X4123

Y7X4123

Y8X4123← Z

Y6X4123

Y1X3

Y4X412

Y5X412

Y3X2

Y4X41

Y1X1

Y4X4

Model C

Lactose crystals homogeneity coefficient when priming material size is 3-4 µm

Results

Silic

on d

ioxi

de

Tita

nium

dio

xide

Cal

cium

car

bona

te

0

2

4

6

8

Lact

ose

crys

tals

size

, µm

0.082 0.089 0.098

Dosage of priming material, %Y14X5

Y13X5

Y11 X5

Y9X4123

Y7X4123

Y8X4123

Y6X4123

Y1X3

Y4X412

Y5X412

Y3X2

Y4X41

Y1X1

Y4X4← Z

Model А

Rational dosage of priming material for lactose crystallization by model A

Results

Silic

on d

ioxi

de

Titan

ium

dio

xide

Calci

um ca

rbon

ate

0

2

4

6

8

Lact

ose

crys

tals

size,

µm

0.051 0.061 0.078


Y13X5

Y11 X5

Y9X4123

Y7X4123

Y8X4123

Y6X4123

Y1X3

Y4X412← Z

Y5X412

Y3X2

Y4X41

Y1X1

Y4X4

Model B

Rational dosage of priming material for lactose crystallization by model B

Results

Silic

on d

ioxi

de

Tita

nium

dio

xide

Cal

cium

car

bona

te

0

2

4

6

8

Lact

ose

crys

tals

size

, µm

0.022 0.029 0.031


Y13X5

Y11 X5

Y9X4123

Y7X4123

Y8X4123← Z

Y6X4123

Y1X3

Y4X412

Y5X412

Y3X2

Y4X41

Y1X1

Y4X4

Model C

Rational dosage of priming material for lactose crystallization by model C

Results

Y15 X5

Y13 X5

Y7 X5

Y10 X5

Y11 X5

Y7X4123

Y8X4123← Z

Y6X4123

Y1X3

Y4X412

Y5X412

Y3X2

Y4X41

Y1X1

Y4X4

Model C/

Thermal treatment at 117 0С during 1 hour

Uncontrolled cooling at room temperature

Germs adding0,03% to products mass

Packing in metal cans №7 (0,4 kg)

Operative model of packaged product lactose crystallization after its thermal treatment

Results

U = 0.64М = ∑na / ∑n = 6.98Y15 X5

Y13 X5

∑nv2=484.1--∑an=698∑n=100∆a = 2Y7 X5

Y10 X5

----0≥ 25IVY11 X5

----024Y7X4123

----022Y8X4123← Z

----020Y6X4123

----018Y1X3

----016

III

Y4X412

49.349.287.0214114Y5X412

100.825.205.0248412II

Y3X2

36.59.123.0240410Y4X41

53.11.041.02408518Y1X1

13.50.960.9884146Y4X4

230.98.882.98104264

I

C/

nv2v2Discrepancy, v

Productna

Crystals frequency, n

Crystals size, а, µm

Crystals groupModel

Results of packaged product lactose crystallization after its thermal treatment

Results

----500.0000,827,090,031CaCO3

----≥770.0000,855,670,029TiO2

500.0000.646.980,022≥770.0000,884,480,022SiO2

M, in 1mm3UD, µmК, %M, in 1mm3UD, µmК, %

C/C

Variant of modification of germs adding timePriming material type

(1-2µm)

270.0000,597,680,078220.0000,419,130,098CaCO3

500.0000,636,860,061270.0000,548,260,089TiO2

500.0000,826,650,051770.0000,766,410,082SiO2

M, in 1mm3UD, µmК, %M, in 1mm3UD,µmК, %

BА

Variant of modification of germs adding timePriming material type

(1-2µm)

Results of lactose crystallization depending on the operating model and priming material type

SiO2>TiO2>CaCO3Efficacy gradation

Results

Farther investigations algorithm Priming material choice

Physico-chemicalproperties

Security

Technologicalpeculiarities

Modeling systems

Development of product technology

Availability

Investigation methodsPRODUCT

Products indices

Preservation stability

Security

Technological parameters

Technological regulations

Economical expediency

Methods of control

Crystallography

Methods of control

Formationconformity

Growth conformity

Efficacy

Production approval

Thank you for attention!Спасибо за внимание!

Aram Galstyan

GNU All-Russia Dairy Research Institute, Moscow, RussiaDepartment of gerodietical and special products

Tel/Fax: +7 (495) 236-02-36www.vnimi.org

E-mail: [email protected]

Acknowledgements

Academician Kharitonov V.DProfessor Radaeva I. A.Chief of the laboratory Petrov A. N.

All colleagues and staff at the Department of Gerodietical

and special products


IDF International Symposium -Lactose and its Derivatives

Analytical Methods for Lactose Quantification in Milk and Milk Products

Rachid Kouaouci, Ing., M.Sc., ChemistValacta, Ste-Anne de Bellevue, Québec, Canada

Centre d’expertise en production laitière du Québec


METHODS

Mid-infraredPolarimetryGravimetryEnzymatic essayDifferential pHChromatography ( HPLC )


MID-INFRAREDIDF 141C:2000; AOAC 972.16

Principle: Measurement of the absorption of the hydroxyl group (OH) at 9.6 µm.

Advantages:Very fast (400 samples/hour)No sample preparationWidely used

Disadvantages:Indirect methodNo differentiation between carbohydratesLimitation to fluid samples


POLARIMETRYAOAC 896.01

Principle:1-Precipatation of fat and protein2-Measurement of the specific rotation of the polarized

light due to the asymmetric carbon of lactose

Advantages:Costs

Disadvantages:Interference with optically active components No differentiation between carbohydratesEmpirical calculation


POLARIMETRYAOAC 896.01

Calculation:C [g/100ml] = a[Vm + Vr – 0.01145Vm ( F+P) ]

Vm (b)a: observed readingVm: Volume of milk usedVr: Volume of reagent usedb: rotation in a 40 cm tube of 100 ml solution

containing 1 gram of lactose at t 0C ( b=2.096at 25 0C)

F: %fat P: % protein


GRAVIMETRYAOAC 930.28

Principle: Lactose + CuSO4

Advantages:Very simple procedureCosts

Disadvantages:Empirical calculationInterference with all reducing carbohydratesNo differentiation between carbohydrates

Cu2O


GRAVIMETRYAOAC 930.28

Hammond table for calculating Lactose

7.78.5.

122.2.

342.0

11.312.4

.179.0

.489.7

Lactose.H2O(mg)

Cu2O(mg)


ENZYMATIC ESSAYIDF 79-1,2/ISO 5765-1,2 (2002); AOAC 930.28

Principle: 1- Lactose

2- β-Galactose + β-Galactose dehydrogenase

+NAD+ (nicotinamide Adenine-dinucleotide)

NADH

3-Measurment of the amount of NADH by absorbance at 340 nm

+ β-GalactosidaseGlucose + β-Galactose


ENZYMATIC ESSAYIDF 79-1,2/ISO 5765-1,2 (2002); AOAC 930.28

Advantages:CostsSolid samples can be used

Disadvantages:More elaborate procedureNo differentiation between carbohydrates


Differential pHIDF/ISO draft

Principle:1- Lactose Glucose + β-Galactose2- Glucose + ATP + Glucokinase

Glucose-6P + ADP + H+

3- Measurement of the pH

+ β-Galactosidase


HPLCIDF 198 │ISO 22622 (FDIS)

• Principle: 1-Sample + Internal Std1

2-Filtration of the sample3-Injection through an analytical column4-Detection by a differential refractometer5-Quantification

+ Biggs Solution2Precipitation of fat

and protein

2Zinc acetate + Glacial acetic acid+ Phosphotungstic acid1Internal Std: Melezitose ( Glu-Fru-Fru )



Chromatographic conditions:Mobile phase: degassed HPLC grade waterFlow rate: 0.6ml / minInternal detector temperature: 350 CColumn temperature: 850 CVolume to be injected: 20 µlRun time: 15 minColumn type: Styrene divinylbenzene resin



Chromatogram of raw milk sample



Chromatogram of raw milk sample with added lactulose



Chromatogram of lactose-reduced milk sample



Chromatogram of raw milk sample with added sucrose and fructose



Advantages:Direct methodDifferentiation between carbohydratesAutomated methodReference methodFlexibility

Disadvantages:Costs


HPLCIDF 198 │ISO 22622 (DIS)


HPLC

IDF 198 │ISO 22622 (DIS)










REFERENCES

• Brons, C, and Olieman, C, 1983. Study of the high performance liquid chromatography separation of reducing sugars applied to the determination of lactose in milk, J. Chromato., 259, 79.

• IDF 141C:2000 -Whole Milk- Determination of milkfat, protein and lactose content, Guidance on the operation of Mid-infrared instruments.

• IDF 79-1:2002│ISO 5765-1- Dried milk, dried ice-mixes and processed cheese- Determination of lactose content- Part 1: Enzymatic method utilizing the glucose moiety of the lactose.

• IDF 79-2:2002│ISO 5765-2- Dried milk, dried ice-mixes and processed cheese- Determination of lactose content- Part 2: Enzymatic method utilizing the galactose moiety of the lactose.

• IDF 106:2004│ISO 5548- Caseins and caseinates- Determination of lactose content- Photometric method.

• Official Methods of Analysis, 16th Ed., 4th Revision, 1998, AOAC INTERNATIONAL, Gaithersburg, MD, methods 896.01, 984.15, 930.28 and 972.16.

• Nickerson, T. A., Vujicic, I. F., and Lin, A. Y, 1976. Colorimetric estimation of lactose and its hydrolytic products. J. Dairy Sci., 59, 386.


Many thanks for your attention!

Hi, I need to measure my lactose level!


Primary Nucleation of Alpha Lactose Monohydrate: The Effect of Supersaturation

and Temperature

J.S McLeod, A.H.J Paterson, JR Jones and JE Bronlund

Nucleation – The effect on crystal size

Nucleation Mechanisms

Primary Nucleation Mechanisms

Primary nucleation equations

3 2

3 2

16exp3( ) (ln )

mHom

K R

VJ AkT S

πσ⎛ ⎞= −⎜ ⎟

⎝ ⎠

3 2

3 2

16 ( )exp3( ) (ln )

mHen

K R

V qJ AkT S

πσ⎛ ⎞= −⎜ ⎟

⎝ ⎠

T Hom HenJ J J= +

Lactose Nucleation – Previous Work

“In the manufacture of lactose it is desirable to secure a maximum yield of crystals in a minimum time, and to secure crystals which may be readily washed with a minimum of loss.” Herrington, (1934)

Effect of Supersaturation on Nucleation Shi, (1990), Griffith, (1982), Kauter, (2003), and Butler (1998)

Effect of temperature on nucleation (Shi, 1990)

Effect of temperature on nucleation (Kauter, 2003)

Experimental Setup

Relating induction time to the nucleation rate

NN

T

NtJ

∝

3 2

3 2

16exp3( ) (ln )

N N mN

K R

N N VtJ A kT S

πσ⎛ ⎞= = −⎜ ⎟

⎝ ⎠

Typical absorbance curve for nucleation

Time to reach critical absorbance vs. supersaturation

The effect of temperature on nucleation rates at different absolute supersaturations

Primary Nucleation Mechanisms

-2 -2Hen R Hom R(-B [lnS ] ) (-B [lnS ] )

N Hen Homt = A exp +A exp× ×× ×

Nucleation Results 25 Degrees




Effect of temperature on the point where the homogenous nucleation begins to appear

20.671.972.176020.102.271.485020.122.711.014020.203.690.5925

Absolute SupersaturationCα-Cαs (g /100 g water)

Relative Supersaturation(Cα/Cαs)

(lnSR)-2Temperature °C

Conclusions

Increasing the supersaturation increases the nucleation rate of alpha lactose monohydrate

The effect of temperature on the nucleation rate at high supersaturations is negligible – temperature becomes more important as supersaturation is decreased

The point at which homogenous nucleation appears as an importantmechanism is independent of temperature (when viewed in absolutesupersaturation).

THANK YOU

Funding and Support

New Zealand Foundation for Research Science and Technology

Fonterra

Massey University

NZIFST (Dairy Division)


Analysis of a sticky impurity:lactose phosphate: a contaminant of

lactose

Dr. Rob Sleigh,Food Science Australia.

Estelle Lifran, Dr. Jim Hourigan, Dr. Rosalie Durham, Dr. Linh Vu,

Centre for Plant and Food Sciences, UWS.

16th May 2007

IDF symposium

Lactose & its derivatives

Role of lactose-phosphate in lactose crystallisation

Lactose phosphate: strong inhibition effect on lactose crystal growth(Visser 1980, 1984 and 1988)

Pharmaceutical grade lactose contaminated by 270 to 400ppm lactose phosphate; preferentially integrated in the crystals; can not be washed off.

→ Impact for industrial crystallisation:Poor control of particle size, size distributions and yield.

New IEL lactose is free of lactose phosphate and other impurities; used as the control in this work.

Study also relevant to pre-crystallisation of spray-dried lactose and dairy powders.

Aim: to control lactose processing in a way relevant to the factory scale; to understand the impact of seeding and impurities on lactose crystallisation kinetics.

alpha-lactose

lactose-phosphate

O

OHOH

HH

H

H

HOH

OH

O

O

OH

HH

OH

H H

OHH

OH

O

OHOH

HH

H

H

HOH

OP

OH

OHO

O

O

OH

HH

OH

H H

OHH

OH

Crystallisation inhibition by lactose phosphate

alpha-lactose

lactose-phosphate

O

OHOH

HH

H

H

HOH

OH

O

O

OH

HH

OH

H H

OHH

OH

O

OHOH

HH

H

H

HOH

OP

OH

OHO

O

O

OH

HH

OH

H H

OHH

OH

0 5 10 15 20 25

50

100

150

200

250

300

Median size (µm)

0 5 10 15 20 25

50

100

150

200

250

300

Median size (µm)

Time (h)

(1) Commercial Pharmaceutical grade(2) Ultra-pure lactose + 60 ppm LP and (3) Ultra-pure lactose (control)

(1)

(2)

(3)

Fast cooling

Fast cooling (1) with 0.4% seeds

(1) with 1% seeds

0 5 10 15 20 250

0.1

0.2

0.3

Solid content (g/g)

0 5 10 15 20 250

0.1

0.2

0.3

Solid content (g/g)

Time (h)

(1)

(2)

(3)

(1) Commercial pharmaceutical grade(2) Ultra-pure lactose + 60 ppm LP and (3) Ultra-pure lactose (control)

(1) with 1% seeds

(1) with 0.4% seeds Fast cooling

Fast cooling

Analysis of the different forms of phosphorus in lactose

Total phosphorus (P):

- ICP-AES

- Spectrophotometric method (FIL-IDF 42B, 1990)

Inorganic phosphorus (Pi):

- Spectrophotometric method (Chen, 1956; FIL-IDF 42B, 1990)

- Same spectrophotometric method under milder conditions (Lowry et al., 1953; Chen, 1956)

- Flow Injection Analysis (FIA) (automated version)

Organic phosphorus/lactose phosphate:

- Indirect: difference between P and Pi

- Direct: CE

Total P content of dairy powders measured by ICP-AES

Concentrations in mg/kg powder (ppm), n= 2

Mineral Skim milk Whey Edible grade Pharma grade Pharma grade Pharma grade Pharma grade Ultra-pure(ppm) powder powder lactose β-lactose 1_1 1_2 2 lactoseCa 11917 6046 1000 22 76 1 12 4K 17334 14107 124 72 18 34 4 0Mg 1047 1058 129 4 3 2 1 0Na 3611 4534 138 72 2 21 3.1 0P 10834 6550 438 37 35 26 19 0Sulphated ash (%) 9.54 7.12 0.320 0.0500 0.0300 0.0200 0.0100 0

Similar results found with spectrophotometric method (FIL-IDF 42B, 1990)

Large variations of total phosphorus content depending on manufacturer and batch of lactose

Determination of the inorganic phosphorus content of lactose powders

Reference methods: Fiske & Subbarow, 1925. Modified by Lowry, 1946, 1953, and Chen et al., 1956, FIL-IDF42B, 1990.

Principle: sulfuric acid + ascorbic acid + ammonium molybdate added to sample, incubated at 38°C for 2 hours, develops blue colour.

The inorganic phosphate ions and molybdate ions form molybdophosphoric acid. This acid is reduced to phosphomolybdenumblue, the concentration of which is measured by spectrophotometry.

The blue colour produced is proportional to the inorganic phosphorus concentration.

Inorganic phosphorus content of dairy powders (n = 10)

No blue colour formationUltra-pure lactose

1.10 ± 01.10 ± 0.21.10 ± 0.1Pharmaceutical grade α-lactose 2

1.77 ± 0.051.50 ± 0.11.78 ± 0.1Pharmaceutical grade α-lactose 1 Batch 1

2.05 ± 0.071.85 ± 0.12.01 ± 0.1Pharmaceutical grade α-lactose 1 Batch 2

2.25 ± 0.21.95 ± 0.42.40 ± 0.3Pharmaceutical grade β-lactose

137 ± 3.5103 ± 4.1145 ± 4.8Edible grade lactose

1840 ± 281833 ± 421850 ± 45Whey powder

2195 ± 642012 ± 732226 ± 98Skim milk powder

FIA(ppm)

pH 4(ppm)

IDF(ppm)

Sample

ppm: mg phosphorus per kg powder

IDF: FIL-IDF42B, 1990, pH = 0.85

pH 4: Lowry et al., 1953

FIA: Flow Injection Analysis, automatic spectrophotometric method

Direct analysis of lactose phosphate in dairy products by capillary electrophoresis (CE)

Method for analysis of anionic compounds (Soga and Imaizumi, 2001; Izco et al., 2003).

Direct detection of lactose-phosphate, Pi and carbohydrates present in samples in one analysis.

Method applied to lactose, cheese, whey and milk

Development of a direct method of analysis of dairy powders by CE

Uses indirect UV detection mode with 20mM PDC + 0.5mM CTAB asbackground electrolyte, optimisation of temperature, pH and injection pressure

Can analyse lactose phosphate in the presence of lactose and other organic compounds without pre-treatment or risk of overloading

Calibration and validation

Lactose phosphate from lactose

Lactose-1-phosphate standards

y = 9755.1x - 51.816R2 = 0.9979

0

2000

4000

6000

8000

10000

12000

0 0.5 1 1.5

Lactose-1-phosphate concentration (mM)

AU day 1

day 2day 3

Lactose-1-phosphate standards (0.9 to 2.4mM)

Small intra-day (0.5%) and day to day (2.7%)variations

Linearity, precision and accuracy all within the range of similar studies

(Castro et al. 1989; Izco et al., 2003)

Analysis of lactose phosphate in lactose powders

Lactose phosphateLactose-1-phosphate

lactose

Citrates

Inorganic phosphates

Commercial pharmaceutical grade lactose powders

IEL lactose

1. IEL lactose free of lactose phosphate

2. Quantification of lactose phosphate in lactose samples using CE

Determination of the lactose phosphate content of lactose powders by CE

Sample Lactose phosphate

(ppm)

Edible grade lactose 368 ± 6

Pharmaceutical grade β-lactose 250 ± 4.8

Pharmaceutical grade α-lactose 1 Batch 2 252 ± 3.9

Pharmaceutical grade α-lactose 1 Batch 1 204 ± 3.7

Pharmaceutical grade α-lactose 2 144 ± 2.5

Ultra-pure lactose No detectable peak

Results expressed as means ± standard deviations, n = 10

ppm: mg lactose phosphate per kg lactose powder

Results are lower than in Visser (1988) estimation of lactose phosphate in batches of pharmaceutical grade lactose (: 270 to 400 ppm)

Determination of the organic phosphorus content of lactose powders by difference

Sample Pa

(ppm) Pi

a (ppm)

Poa

(ppm)

Lactose phosphateb

(ppm)

Edible grade lactose 438 103 335 4556

Pharmaceutical grade β-lactose 37 1.9 35 476

Pharmaceutical grade α-lactose 1 Batch 2 35 1.8 33 449

Pharmaceutical grade α-lactose 1 Batch 1 26 1.5 24 326

Pharmaceutical grade α-lactose 2 19 1.1 18 245

Ultra-pure lactose No blue colour formation

a expressed in mg of phosphorus per kg of lactose

b expressed in mg of lactose phosphate per kg of lactose

- =

To be compared to the value found by the direct method368

250

252

204

144

All the organic phosphorus present in lactose samples is not lactose phosphate as was previously assumed

Other sources of organic phosphorus exist

Analysis of lactose phosphate extracted from lactose by HPAEC-PAD

1,2 and 3:

Unknown peaks

4: Lactose phosphate

5: N-acetylneuraminic acid

6: KDN

Both sialic acid analogues

Showing pharmaceutical grade lactose contains other acidic components, especially GOS

Impurities other than lactose phosphate could also be phosphorylated

High performance anion exchange chromatography with pulsed amperometricdetection

Very sensitive, down to picomoles (1x10-12

moles)

Need extensive pre-treatment of lactose samples before analysis

Causing loss of lactose phosphate therefore no quantification possible for impure samples

Summary

Analysis of the different forms of phosphorus in lactose powders

1. Suitability of the spectrophotometric method to measure totaland inorganic phosphorus, in the absence of organic phosphates

2. Lactose phosphate can not be quantified indirectly

3. Lactose phosphate can be analysed in lactose and other dairy products by CE

4. Lactose phosphate is only one of several acidic contaminants present in traces (picomole order) in pharmaceutical grade lactose

CE was used as a tool to monitor lactose phosphate integration

During seeded batch isothermal and cooling crystallisations (Lifran et al.,Powder technology (2006), doi:10.1016/j.powtec.2006.11.010).

Acknowledgements

We would like to thank Food Science Australia, the Centre for Plant and Food Sciences of the University of Western Sydney and Dairy Australia for their support of the project.

Special Thanks to Estelle Lifran, Linh Vu, Jim Hourigan, and Rosalie Durham.

Thank You For Your Attention


COMPUTER MODELLING COMPUTER MODELLING AND FORECASTING OF AND FORECASTING OF

PHYSICAL AND CHEMICAL PHYSICAL AND CHEMICAL PROPERTIES OF LACTOSEPROPERTIES OF LACTOSE

A.V.SEROVA.V.SEROVNorthNorth--Caucasian State Technical Caucasian State Technical

UniversityUniversityStavropolStavropol, , RUSSIARUSSIA

112,3112,3113,8113,8109,9109,9110,0110,0114,9114,9113,6113,6108,2108,2105,6105,6110,1110,1110,7110,7109,7109,7109,7109,7110,1110,1112,7112,7114,3114,3104,5104,5109,9109,9117,5117,5

113,8113,8110,2110,2112.9112.9112.2112.2120,3120,3117,6117,6102,7102,7109,3109,3110,0110,0111,6111,6111,8111,8113,9113,9113,1113,1112,1112,1116,4116,4112,7112,7115,3115,3117,0117,0

110,9110,9110,9110,9108,9108,9109,0109,0112,2112,2111,2111,2107,0107,0107,7107,7108,8108,8110,5110,5108,1108,1111,4111,4110,0110,0108,4108,4112,0112,0106,8106,8110,3110,3117,1117,1

GalactoseGalactose residueresidueСС(1(1''))--СС(2(2''))--СС(3(3''))СС(2(2''))--СС(3(3''))--СС(4(4''))СС(3(3''))--СС(4(4''))--СС(5(5''))СС(4(4''))--СС(5(5''))--ОО(5(5''))СС(5(5''))--ОО(5(5''))--СС(1(1''))ОО(5(5''))--СС(1(1''))--СС(2(2''))ОО(5(5''))--СС(1(1''))--ОО(1(1''))СС(2(2''))--СС(1(1''))--ОО(1(1''))СС(1(1''))--СС(2(2''))--ОО(2(2''))СС(3(3''))--СС(2(2''))--ОО(2(2''))СС(2(2''))--СС(3(3''))--ОО(3(3''))СС(4(4''))--СС(3(3''))--ОО(3(3''))СС(3(3''))--СС(4(4''))--ОО(4(4''))СС(5(5''))--СС(4(4''))--ОО(4(4''))СС(4(4''))--СС(5(5''))--СС(6(6''))ОО(5(5''))--СС(5(5''))--СС(6(6''))СС(5(5''))--СС(6(6''))--ОО(6(6''))GlycosidicGlycosidic lincagelincageСС(1(1''))--ОО(1(1''))--СС(4)(4)

АМАМ11РМРМ33Experiment byExperiment by KK. . HirotsuHirotsuandandAA. . ShimadaShimada

AngleAngle

Table 1 Table 1 -- Dependence of Dependence of valentvalent angles values in the angles values in the method of optimization of method of optimization of αα--lactose moleculelactose molecule

Table 1 Table 1 -- Dependence of Dependence of valentvalent angles values in the angles values in the method of optimization of method of optimization of αα--lactose moleculelactose molecule

((continue)continue)

108,9108,9108,9108,9109,6109,6112,1112,1114,3114,3112,0112,0103,6103,6110,9110,9112,2112,2110,9110,9112,5112,5109,0109,0112,6112,6105,3105,3111,0111,0106,5106,5111,3111,3

112,2112,2110,5110,5111,2111,2111,9111,9116,3116,3113,0113,0107,9107,9109,3109,3112,3112,3111,6111,6110,1110,1106,3106,3109,6109,6104,4104,4111,7111,7104,6104,6112,2112,2

110,9110,9110,3110,3111,1111,1107,9107,9114,1114,1109,7109,7111,5111,5108,8108,8111,1111,1112,7112,7107,0107,0111,6111,6110,6110,6107,0107,0113,7113,7107,2107,2111,2111,2

Glucose residueGlucose residueСС(1)(1)--СС(2)(2)--СС(3)(3)СС(2)(2)--СС(3)(3)--СС(4)(4)СС(3)(3)--СС(4)(4)--СС(5)(5)СС(4)(4)--СС(5)(5)--ОО(5)(5)СС(5)(5)--ОО(5)(5)--СС(1)(1)ОО(5)(5)--СС(1)(1)--СС(2)(2)ОО(5)(5)--СС(1)(1)--ОО(1)(1)СС(2)(2)--СС(1)(1)--ОО(1)(1)СС(1)(1)--СС(2)(2)--ОО(2)(2)СС(3)(3)--СС(2)(2)--ОО(2)(2)СС(2)(2)--СС(3)(3)--ОО(3)(3)СС(4)(4)--СС(3)(3)--ОО(3)(3)СС(3)(3)--СС(4)(4)--ОО(1(1´́))СС(5)(5)--СС(4)(4)--ОО(1(1´́))СС(4)(4)--СС(5)(5)--СС(6)(6)ОО(5)(5)--СС(5)(5)--СС(6)(6)СС(5)(5)--СС(6)(6)--ОО(6)(6)

АМАМ11РМРМ33Experiment byExperiment by KK. . HirotsuHirotsu andandAA. . ShimadaShimada

AngleAngle

Fig 1 Alpha-lactose molecule after semiempirical method optimization in АМ1 parametrization on Polak-Ribiere algorithm

Fig 2. Values of an effective charge of alphaFig 2. Values of an effective charge of alpha--lactose molecule atoms and its lactose molecule atoms and its formation heat after geometrical optimization by means of formation heat after geometrical optimization by means of semiempiricalsemiempirical

method in method in АМАМ1 1 parametrizationparametrization on on PolakPolak--RibiereRibiere algorithmalgorithm

Fig. 3 Map of distribution of molecular electrostatic potential Fig. 3 Map of distribution of molecular electrostatic potential of of αα--lactose moleculelactose molecule

Fig. 4 Map of threeFig. 4 Map of three--dimensional distribution of dimensional distribution of molecular electrostatic potential of molecular electrostatic potential of αα--lactose moleculelactose molecule

Fig 5 MetalFig 5 Metal--organic complexorganic complex

OH H

H

H

H

C C

O

CO

Ca++

Figure 6 Figure 6 -- Structure of complexStructure of complex tetrahydroxoboratetetrahydroxoborate--lactoselactose

Fig. 7 Fig. 7 -- Possible Possible isomerizationisomerization mechanism of lactose at presence of a mechanism of lactose at presence of a tetrahydroxoboratetetrahydroxoborate--ionion

Figure 8 Figure 8 -- Spectrum of the 13Spectrum of the 13СС nuclear magnetic resonance of nuclear magnetic resonance of anomericanomeric centers in the equilibrium centers in the equilibrium lactuloselactulose solutionsolution


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