mechem for agric

8/11/2019 Mechem for Agric

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MECHANOCHEMISTRY FOR AGRICULTURE: SOLUTION OFECOLOGICAL PROBLEMS, INNOVATIONS, NEW

TECHNOLOGIES, NE BIOLOGICALLY ACTIVE COMPOUNDS

Oleg Lomovsky, Kirill Korolev, V. SalenkoInstitut of Solid State Chemistry SB RAS,BIZAR, NovosibirskChair of Solid State Chemistry Novosibirsk State University

1. Intercellular materials - cellulose, pectin, humic2. Cell wall materials lipids, MOS

3. Cellular materials bioactive compounds


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The most effective mechanochemicaltechnology combines physical and chemical

transformation with milling operation


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1. Intercellular materials


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Properties of carboxymethylcellulose (CMC)

from corn straw

Initial Standard Straw

Water return,

cm3/ 30 m 16 8 7Filtration,

mm 2.5 1.5 1.0Effective visco-sity, mPa.s 18.5 20 20Static shift

intensity, dPa 19 57 57Dynamic shift

intensity, dPa 93 168 62Density,

g/cm3 1.070 1.070 1.078pH 8 9 9.5

Fresh water clay drillingsolution 1 m3 + 0.53 kgstandard CMC or 1.6 kg of

mechanochemical strawCMC

Lomovsk , Fadeev, 2003


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Pectin gel forming agent

from plant raw

Viscosity, mPas, under 20 C

Concentration,

mass%

Without

heating

Heating,

24 hrs, 80 C

Week after

heating

5 6.8 20.0 6.0

7 37.7 156 56.7

10 851.7 no viscosity no viscosity

Viscosity of water solutions of mechanicallytreated sunflower pectin materials

Altunina, Lomovsky et al., 2003


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2. Cell components, role of lipids

Tannins from pine bark

Lomovsky, Belykh, 2000


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3. Cellular Materials - Biologically ActiveCompounds:

alkaloids, acids, glycosides, phytosterols

Extraction bywater

Soluble salts andcomplexes

Molecular complexeswith soluble matrix

Glycosides

Extraction byorganic solvents

Purification Purification

Raw Plant Materials

Grinding Mechanochemicalreactions of BACs

+ Solid Reagent

Product Product NewProduct

Solublebioavalaible formsof BACs:


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BallastCompounds

BallastCompounds

Traditional Technology of BACs Productionfrom Plant Materials

Alkaloids, acids, glycosides, phytosterols

SolventsRaw Plant

materials

BACs and Ballast Compounds

`

Purification


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Aconitum roots

Extract 1

Extract 2

Acid extract 3

Acid extract 4

Sum of alkaloids

Medicinalproduct, 0.3%

Infusionacetone/water

Chromatography Al2O3methanol, ethanol

pH9, CHCl3

5% H2SO4

Washing CHCl3

CHCl3 ethanol

Aconitum roots

+ Solid phase

Reaction mass

Sum of alkaloids

Mechanochemicalprocessing

Extraction

HBr ethanol

Medicinalproduct, 1.3%

OCH3

OCH3

OH

O

OCH3

NC2H5

O

NHCOCH3

HO

Traditional method Mechanochemical approach

Alkaloid Allapininum Production Schemes

Pankrushina, Lomovsk et al., 2002


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YIELDS of Biologically Active Compounds,

Traditional Technique, %, New Technique, %

Berberine(Isoquinoline alkaloid)

0.8/2.0

Theobromine (Puryne alkaloid)

0.5/1.3

Alantolactone Isoalantolactone

2.0/5.0

3--D-digytoxose-4- -D-xylose

Erychroside(Cardiac glycoside)

0.014/0.04

Triterpenoid acids

2.5/4.5


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The Main Mechanochemical Reactions Used forSolubilization and Mechanochemically Assisted Extraction

Soluble Salts by Acid-Base Transformations

... with Tautomeric Transformations

Formation of glycosides

-hydroxylactone

Formation of Complexes

nGLU + St-OH nGLUSt-OH


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Selectivity of mechanochemical processing

High-performance Liquid Chromatography Data

Extract of Reaction Mass afterMechanochemical Processing

Extract of Aconitum Roots,

Traditional Technology

Mechanochemically assisted extraction of Lappaconitine

Pankrushina, Lomovsky et al., 2002


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Biologically Active Compounds:

alkaloids, acids, glycosides, phytosterols

Extraction bywater

Soluble salts andcomplexes

Molecular complexeswith soluble matrix

Glycosides

Extraction byorganic solvents

Purification Purification

Raw Plant Materials

Grinding Mechanochemicalreactions of BACs

+ Solid Reagent

Product Product NewProduct

Solublebioavalaible forms

of BACs:


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HO

H

H

H

HO

H

H

H

Mechanochemical Solubilization

Phytosterol Feed Additives for Agriculture Animals

Technology

Utilization

(a) (b)

a) Usual additives

b) Phytosterol additives bymechanochemical method

Solubility (bioavailability)of our feed additives

(A) standard sample mixture(campesterol and -sitosterol); (B) mechanochemical product, yield ofwater-soluble forms; (C) the controlwithout mechanochemical processing.

+15% - +20%

Lomovsky,Salenko, 2002

Mechanochemically Assisted Extraction of


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Mechanochemically Assisted Extraction of

Phytoecdystreroids

Natural Anabolic Preparations for Agricultural Animals

Utilization of the preparationscontaining phytoecdysteroids

Technology

Perspective stimulators inbreeding animals

Growth promoters without anyhormonal consequences

Boosting protein biosynthesis inliver, muscular tissues

Restoration of animal genesialfunctions

Powderpreparation

Selectiveprecipitationof 20E fromwater extract

Effectiveextraction ofother

ecdysteroids

OH

OH

OH

OH

O

OHOH

OH

OH

OH

O

OH

OH

OH

Lomovsky, Korolyov, 2003

N t l G th Sti l t f Pl t C lti ti T it id A id


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Natural Growth Stimulators for Plant Cultivation Triterpenoid Acids

from Siberian Pine

The Mechanochemical approach

Promoting plants growth and reducingmaturing period of ones

Increasing plants productivity Natural ecologically pure growthstimulator

Perspective accelerators for microbiology

Utilization

Technology Biologically activewater extracts

Biologically activepowder preparations

for germination of

seeds

Advantages ofmechanochemical processing

Selectivity High yield

Korolyov, Lomovsky et al., 2003

N l G h S i l f Pl C l i i


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Natural Growth Stimulators for Plant Cultivation

Triterpenoid acids from Siberian FirThe outcomes of MS-HPLC APCI Neg. Scan [M-H]

The known way Mechanochemical approach

Korolyov, Lomovsky et al., 2004

N t l G th Sti l t f Pl t C lti ti


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Natural Growth Stimulators for Plant Cultivation

The outcomes of biological tests

Utilization

For seedling stage of wheat:

seed germinating +10%

rootlet formation +29%

often leaf-bearing plants

developing +18%

O

H

HOOC

O

O

H

COOH

O

Rozhanskaya, Korolyov, Lomovsky, 2004


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Not every mill can be used as mechanochemicalreactor


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Special Mechanochemical Equipment

Vibratory-Centrifugal Mill VCM-20


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Special Mechanochemical Equipment

VCM and CEM Mills

, 600 , 50 , 20 , 140 .

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