Biosynthetic relations of sugars and further secondary
metabolites
Glucose
H2OCO2 hν
Phospho-enol pyruvate
Erythrose-4-phosphate
Shikimic acid
Shikimates
Pyruvate
Acetyl-CoA
Aminoacids
Alkaloids
Mevalonate
Terpenoids and steroids
Acetogenines
Glycosides
photosynthesis
Flavonoids, anthocyanins
tannins…
Derivatives of cinnamic acid
Lignans
Coumarins
Quinones
Proteins
Mono, oligo, polysaccharides
Phenols, quinones,
polyacetylenes, macrolides,
fatty acids, lipids…
Essential oils, sesquiterpenes, diterpenes,
saponins, cardenolides, carotenoids…
cycle
SACCHARIDES – CARBOHYDRATES – SUGARS
UNIVERSAL COMPONENTS OF LIVING ORGANISMS
COMPOUNDS POSSESSING:
• CARBONYL GROUP (ALDEHYDE OR KETONE)
• MORE HYDROXYL GROUPS
CAN POSSESS
• OXIDIZED CARBONYL (URONIC ACIDS)
• REDUCED CARBONYL (POLYALCOHOLS)
• DERIVATIVES (ETHERS, ESTERS, AMINES)
FUNCTION IN PLANTS
• SUPPORTING SUBSTANCES (CELLULOSE A OTHER
„BUILDING“ POLYSACCHARIDES)
• ENERGY POOL (STARCH)
• PART OF DIFFERENT METABOLITES (NUCLEIC ACIDS,
COENZYMES, GLYCOSIDES)
• NECCESSARY PRECURSORS OF ALL OTHER METABOLITES OF
THE LIVING WORLD
CLASSICAL DIVISION
• MONOSACCHARIDES Cn(H2O)n
• (n-1) HYDROXYL GROUPS (EXCEPTION DEOXYSUGARS = (n-2))
• ALDEHYDIC or KETONE CARBONYL FUNCTION (aldoses, ketoses)
• NUMBER OF C- ATOMS 3 TO 9, MOSTLY FIVE OR SIX (tetroses,
pentoses, hexoses, heptoses)
• Couplet designation – glucose = aldohexose, ribulosa = ketopentose
• Majority of natural monosaccharides belongs to D-line
• To L-line belong L-rhamnose, L-arabinose, L-fucose
• Abbreviations: glucose – Glc; fructose – Fru; arabinose – Ara; ribose –
Rib; xylose – Xyl; rhamnose – Rha; galactose – Gal; manose – Man;
deoxyribose – deRib; glucuronic acid – GlcUA; galacturonic acid – GalUA;
gluconic acid - GlcA
CLASSICAL DIVISION
OLIGOMERIC SACCHARIDES
GLYCOSIDIC BOND BETWEEN LESS THAN 10 MONOSACCHARIDES
POLYMERIC SACCHARIDES
GLYCOSIDIC BOND BETWEEN MORE THAN 10 MONOSACCHARIDES
COMPOSITE SACCHARIDES
CONTAIN ALSO LIPIDIC, PROTEIN, PEPTIDES
GLYCOSIDES (-O; -N; -S; -C)
USAGE
• MONOSACCHARIDES AND OLIGOSACCHARIDES –
THERAPEUTICALLY LESS IMPORTANT
• POLYSACCHARIDES - PHARMACEUTICALLY AND INDUSTRIALLY
MORE IMPORTANT, AS THE MOTHER PLANTS AND
CORRESPONDING DRUGS
• MANY TIMES DIETETICS AND NUTRITIVES, LESS FOR
PHARMACOLOGY EFFECTS - IMMUNOMODULANTS
CHEMISTRY OF SUGARS
C
O
H
C
C
C
C
H OH
OH
OH
H OH
H
H
CH2OH
C
O
H
C
C
C
C
H OH
OH
OHH
HOH
H
CH2
OH
D-glucose L-glucose
Symbols of D- and L- express absolute configuration at asymetric
carbon atom furthermost from carbonyl group in Fischer projection.
Optic rotation: (+); (-)
CONFIGURATION CONNECTIONS OF D-ALDOS
C
H
COH
COH H
CH OH
CH2
OH
O
H
C
H
CH
COH H
CH OH
CH2
OH
O
OH
C
H
COH
CH OH
CH OH
CH2OH
O
H
C
H
CH
CH OH
CH OH
CH2OH
O
OH
C
H
COH
CH OH
CH2OH
O
H
C
H
CH
CH OH
CH2OH
O
OH
C
H
CH OH
CH2OH
O
C
C
OH H
H O
COH
COH H
CH OH
CH2OH
H
C
C
H OH
H O
COH
COH H
CH OH
CH2
OH
H
C
C
OH H
H O
CH
COH H
CH OH
CH2OH
OH
C
C
H OH
H O
CH
COH H
CH OH
CH2
OH
OH
C
C
OH H
H O
COH
CH OH
CH OH
CH2OH
H
C
C
H OH
H O
COH
CH OH
CH OH
CH2OH
H
C
C
H OH
H O
CH
CH OH
CH OH
CH2OH
OH
C
C
OH H
H O
CH
CH OH
CH OH
CH2OH
OH
D-lyxose D-xylose D-arabinose D-ribose
D-threose D-erythrose
D-glyceraldehyde
D-talose D-galactose D-idose D-gulose D-mannose D-glucose D-altrose D-allose
CONFIGURATION CONNECTIONS OF D-KETOSES
C
CH2OH
O
CH
CH OH
CH OH
CH2OH
OH
C
CH2OH
O
COH
CH OH
CH OH
CH2OH
H
C
CH2OH
O
CH
COH H
CH OH
CH2
OH
OH
C
CH2OH
O
COH
COH H
CH OH
CH2OH
H
C O
CH2
OH
CH
CH OH
CH2
OH
OH
C
CH2OH
O
COH
CH OH
CH2
OH
H
C
CH2
OH
O
CH OH
CH2
OH
D-psicose D-fructose D-sorbose D-tagatose
D-ribulose D-xylulose
D-erythrulose
CHEMISTRY OF SUGARS
Spontanneous intramolecular addition of one from hydroxyl group (primary or
secondary hydroxyl group) on a carbonyl group gives rise to cyclic poloacetals
(pyranoses, furanoses). This reaction produces new chiral centre.
O
H
H
OH
OH
H
H
OH
CH2
OH
H
OH
O
H
OH
H
H
OH
CH2
OH
OH H
H OH
C OHH
C
C
C
C
CH2
OH
OH
OH
H
OH
O
H
H
H
C OHH
C
C
C
C
CH2
OH
OH
OH
H
O
H
H
OH HC
C
C
C
C
CH2
OH
OH
OH
H
OH
OH
H
H
H
H O
-D-glucopyranose -D-glucopyranose
cis = anomer trans =anomer
1
1
1 1
D-glucose
1
CHEMISTRY OF SUGARS
In crystal form monosaccharides exist exclusively in cyclic structures, therefore as α- or β-anomers
O
CH2OH
H
OH
H
O
H
CH2OH
OHOH
H
CHO
OH
H
H
HOH HOH
-D-glucopyranose -D-glucopyranose
 D + 112 0  D
+ 19 0
52.5 0
Mutarotation - spontanneous change of optic rotation of freshly prepared solution of stereomer.
It confirmes the occurence of sugars in cyclic form.
hydrated aldehydic
form of glucose
CHEMISTRY OF SUGARS
Cyclic forms of saccharides are not planar formations. Thermodynamically best conformations of
pyranoses are chair conformation.
H
OH
H
OH OH
H
H
OH
OCH2OH
H
OH OH
H
H
OH
OH
H
OCH2OH
1
2
3
4
5
6
-D-glucopyranose -D-glucopyranose
CHEMISTRY OF SUGARS
O
H
H
OH
OH
H
H
OH
CH2
OH
OH
H
O
H
OH
H
H
OH
CH2
OH
H
OH
H
OH O
H
H
OH
OH
H
OH
H
CH2OH
OH
H
Epimers are isomers, which are different in configuration at one asymetric centre.
-D-glucose -D-galactose -D-mannose
BASIC MONOSACCHARIDES
TETROSES
FOUR possible isomers produces two pairs of enantiomers:
• D- and L-threose
• D- and L-erythrose
They do not occure free.
• D-erythroso-4-phosphate possess key role in formation of aromatics.
• Erythrulose is formed as intermediate for example during
photosynthesis
BASIC MONOSACCHARIDES
PENTOSES
• D-ribose is universal, its phosphates are metabolites of basic
importance, components of nucleic acids and nucleotide coenzymes
• D-ribulose is ketopentose corresponding to ribose, P and P-P esters
found during interconversion of sugars
• D-xylulose = C-3 epimer of ribulose, part of plant polysaccharides
• L-arabinose and D-xylose – usually components of complex
polysaccharides, hemicelluloses, pectines and polymeric plant secrets
(gummms and mucilages). Found also as sugar component of phenolic
glycosides.
BASIC MONOSACCHARIDES
HEXOSES – usually ubiquitous
• D-glukose found in free form (fruits), found in polysaccharides (starch,
cellulose and other glucanes); important are phosphate esters
• D-mannose = C-2 epimer of glucose, component of polysaccharides,
at animals component of glycoproteins, mucopolysaccharides
• D-galactose = C-4 epimer of glucose, component of milk sugar and
oligosaccharides, in agar L-galactose is present
• D-fructose (levulose); free in form of pyranose, furanoid form in
oligosaccharides only (saccharose) and polysaccharides (inuline); part
of honey; P-esters intermediates of glucose metabolism
SPECIFIC MONOSACCHARIDES
DEOXYSUGARS
• 2-deoxyribose – ubiquitous as component of DNA
In plants as sugars, in which were one or two hydroxyl groups eliminated
by reduction – part of some glycosides
• L-rhamnose (6-deoxy-L-mannose) component of heterogeneous
polysaccharides nad of many glycosides
• L-fucose (6-deoxy-L-galactose) as component of Phaeophyceae algae
polymers and chosen gums (Tragacanta)
• D-quinovose (6-deoxy-D-glukosae sugar part of triterpenoid saponine
present in Cinchona
• Some 6-deoxyhexosyes in form of methylethers are specific in
cardioactive glycosides, for example L-thevetose (= 6-deoxy-3-Omethyl-
L-glucose) and D-digitalose (6-deoxy-3-O-methyl-D-galactose)
SPECIFIC MONOSACCHARIDES
O
CH3
OH
OH
OH
OH
O
OH
OH
OH
CH3
O
CH3
OH
OH
MeO
-D-Digitoxose
-L-Oleandrose-L-Rhamnose
URONIC ACIDS
HEXOSES → SPECIFIC DEHYDROGENASES → CH2OH → -COOH
• D-GLUCURONIC ACID
• D-GALAKTURONIC ACID
↓
↓
• PECTINE, GUMS
POLYALCOHOLS
CARBONYL FUNCTION OF MONOSACCHARIDE
→ REDUCTION → POLYALCOHOL
+ 2 H in molecule
Non-reducing Fehling solution
Are not subjects of alcoholic fermentation
The most occurring are D-sorbitol a D-manitol
CH2OH
C
C
C
C
H OH
OH
OH
H OH
H
H
CH2OH
CH2OH
C
C
C
C
OH
OH
H OH
H
OH H
H
CH2
OH
D-Sorbitol D-Manitol
AMINOSUGARS
• BASIC COMPONENTS OF BACTERIAL POLYSACCHARIDES
• COMPONENTS ANTHRACYCLINE ANTIBIOTICS –
CYTOSTATICS (Adriamycine, Daunorubicine, Aclarubicine)
• POLYMERS OF ANTHROPODS AND CRUSTACEANS (CHITINE)
• COMPONENTS OF ANIMAL GLYCOPROTEINS
• IN SOME FUNGI
• RARE IN HIGHER PLANTS
AMINOSUGARS
O
CH2OH
OH
OH
H
NH2
OH
O
CH2OH
OH
H
OH
NH2
OH
O
NH2
OH
OH
OOC
CH
C
CH2OH
H
OH
OH
-D-glucosamine -D-galactosamine
neuraminic
acid(chitosamine) (chondrosamine)
membrane glycolipides
"bifidus factors"
RAMIFIED SUGARS
• OFTEN PRESENT IN FUNGI
• EXCEPTIONALLY IN HIGHER PLANTS (bonded as esters or
glycosides
GLUCOSE
Prepared by enzymatic hydrolysis of starch
using effect of -amylase and
amyloglucosidase
ČL 2009
• Glucosum anhydricum
• Glucosum liquidum
• Glucosum liquidum dispersione
desiccatum
• Glucosum monohydricum
Rigorous test on solubility, neutral character, absence of
starch and dextrin, limit assays to detect presence of
sulphides, chlorides, sulphates and Ba, As, Cd and Pb
O
H
H
OH
OH
H
H
OH
CH2OH
OH
H
-D-glucose
GLUCOSE
Prepared:
• water solutions for parenteral application
• solutions for injection (5% and 10%)
• Hypertonic solutions for injection (15%, 20%, 30% and 50 %)
Used for:
• re-hydration, when loss of water is higher than loss of natrium
chloride and other electrolytes
• prevention of dehydration
• prophylaxis and correction of ketosis during malnutrition
• vehicle for application of drugs in pre- or post surgery period
Solution of glucose are indifferent in caloric intake.
GLUCOSE
Solutions of glucose:
• are administered very slowly
• recommended biologic monitoring (glycosuria, acetonuria, levels of K+
in blood)
• If necessary, supplementation of insulin and potassium
Contraindication in case of water retention.
FRUCTOSE
Prepared by hydrolysis v inuline (Asteraceae) – Helianthus tuberosus –
topinambour, Cichorium intybus – chicory
Present in all fruits and honey
Rigorous assays to control solubility, neutral character, absence of starch and dextrin, limit tests
to detect presence of sulphides, chlorides, sulphates and Ba, As, Cd and Pb
Usage: ČL 2009 Fructosum
• parenteral nutrition
• in diet of diabetics
• Gut resorption is slow, does not trigger secretion of insuline
• metabolisms hepatal
• sweetener – 1.7 × higher sweet taste than saccharose
Helianthus tuberosus Cichorium intybus
D-SORBITOL
Prepared via catalytic hydrogenation under high pressure or
electrolytic reduction of glucose
In nature:
• fruits of Rosaceae plants – Sorbus aucuparia – mountain ash,
European rowan
• insoles of sea algae
ČL 2009
• Sorbitolum
• Sorbitolum 70% cristallisabile
• Sorbitolum 70% non cristallisabile
• Mixtures with aliphatic acids
D-SORBITOL
Usage:
Pro infusione:
• 5% and 10% solution – for rehydration, caloric indifferent, prophylaxis of ketosis,
adjuvant for drug administration
Others:
• cholagogue
• during dyspepsia and as supporting and additive remedy during constipation
• Sweetener for diabetics, metabolized to D-fructose → glycogen
• pharm. technology – regulation of humidity in powders, plasticizer of gelatin,
sugar crystallization retardant
• Food industry – excellent solubility, hygroscopic, non cariogenic, does not
undergo microbial degradation
• EU code: E420
D-MANNITOL
Prepared via D-glucose epimerization under alkaline conditions
and following catalytic or electrolytic reduction
In nature:
• Manna (Fraxinus ornus – manna ash, Oleaceae)
• Insoles of brown algae (Laminaria)
ČL 2009
• Mannitolum
D-MANNITOL
Usage:
Pro infusione:
• intravenous 10% or 20% solution slowly administered during oligouria
and anuria, diuretic – very difficult to metabolize – when parenteraly
administered rapid glomerular filtration and no tubular resorption
Others
• per os – cholecystokinetic, laxative
• preparation of patient for colonoscopy
• Food industry
• EU code: E421
MANNA - MANA
Fraxinus ornus L., manna ash (Oleaceae)
• Occurrence: South Europe
• Used part: Air dried juice obtained by cutting the tree bark
• Collection and adjustment: after drying the excretes are removed and
collected
• Macro: Rounded pieces of whitish and weak yellowish mass, sweet
taste
• Content compounds: Mannitol
• Effect: dilution of gut content
• Usage: mild laxative in pediatrics
Fraxinus ornus L., manna ash (Oleaceae)
MANNA
Starch
Partial hydrolysis Complet hydrolysis
Maltodextrins
Glucose sirups
Fructose sirups
Glusose
Sorbitol
Fructose
Mannitol
Maltose enriched
sirups
Maltitol
STARCH INDUSTRY
MEL - HONEY
Apis mellifica L., honey bee (Apidae)
• Description: From honeycombs obtained liquid, in time grainy
crystalline
• Collection and adjustment: VII-VIII, removal of mechanic admixtures
• Macro: Pale yellow to brown-yellow viscose liquid, characteristic odor,
(lime honey, acacia honey, forest honey), sweet taste
• Content compounds: - invert sugar (80 %)
- glucose, fructose, saccharose
- acetylcholine, choline
- vitamins
- bacteriostatic compounds (traces)
- pollen grain
MEL – HONEY
• Usage: - nutritious and tonic remedy
- during diseases from cold
- sweetener
- mild laxative
• Note: individual intolerance
• MEL FOENICULI
• MEL ANISATI
• GELÉE ROYALE
• PROPOLIS
Apis mellifica
PROPOLIS
Apis mellifica
SUGAR DERIVATIVES
ASCORBIC ACID
O
H
OH
H
H
OH
CH2
OH
OH H
H OH
O
OH
OH
H
O
C HOH
CH2
OH
X
X
*
*
OH
O
O
O
C HOH
CH2OH
ox.
red.
HOH
O
O
OH
OH OH OH
O
-D-glucopyranose
ascorbic acid dehydroascorbic acid
bicyclic hydrated
hemiacetal
L-(+)-threo-askorbic acid
Hippophae rhamnoides L.
Rosa canina L.
Actinidia chinensis Planch. (kiwi)
Capsicum annuum L