La Energía en la Vida

Carbohidratos

Pablo A. Araujo G.
 Para lectura …

Hart
•Capítulo 16

McMurry
•Capítulo 25

Wade
•Capítulo 23
roup.
Carbohydrates are usually classified according to their structure as monosac
¿qué son?
des, oligosaccharides, or polysaccharides. The term saccharide comes from L
accharum, sugar) and refers to the sweet taste of some simple carbohydrates.
hree classes of carbohydrates
• Carbohidrato are related
= Hidrato to each other
de Carbono through hydrolysis.
= Azúcares

• Fórmula generalH2=O Cn(H2O)n H2O

polysaccharide 1 oligosaccharides
H H1
monosaccharides (

• Polihidroxialdehidos
or example, hydrolysis of starch, a polysaccharide, gives first maltose and t
• Polihidroxicetonas
lucose.
• Sustancias que los producen por hidrólisis
n H2O n H2O
[C12H20O10]n H1
n C12H22O11 H1 2n C6H12O6 (
starch maltose glucose
• (aReacciones
polysaccharide)
químicas: (a disaccharide) (a monosaccharide)
• Combinación de ambos grupos (carbonil + hidroxilo)
Monosaccharides (or simple sugars, as they are sometimes called) are carbohydr
hat cannot be hydrolyzed to simpler compounds. Polysaccharides contain m
monosaccharide units—sometimes hundreds or even thousands. Usually, but
 H2O
glucose.
olysis monosaccharides
rides ofH1starch, a polysaccharide
Primera clasificación
n H2
Polisacáridos [C12H20 O10]
accharide, gives first maltose Han
n 1

starch
n H O n H2
Disacáridos
H 1
2
n polysaccharide)
O10]n(Oligosacáridos)
(a C12H22O11 H1
h n H2O maltose
Monosaccharides
O11 Monosacáridos 2n C H(or simple
O su
haride) (a disaccharide)
6 12 6
that
H cannot be hydrolyzed to s
1

e glucose
monosaccharide units—somet
 ¿para qué sirven?

• Energía
• Almacenamiento
• Transporte
ceraldehyde, the simplest
at glyceraldehyde, aldose,aldose,
the simplest has one
hass
n exist
ence caninexist
twoin Quiralidad
enantiomeric forms.forms.
two enantiomeric

CH PCH
O PO CH PCH
O P
A A A A
#OH
H # CH! C ! OH HO #HO
C!#HC ! H
A A A A
CH2OH
CH2OH CH2O
CH2OH
R-(1)-glyceraldehyde S-(2)-glyceraldehyde
1)-glyceraldehyde S-(2)-glyceraldeh
25 25
[a ] D 18.7(c
18.7(c 5 2,H25 25 [a ] D 28.7(c
O)2,H2O)[a ] D 28.7(c O)2,H
5 2,H25
 1 1
CH P O CH2OH CH2
2 A 2
A A
CHOH C PO CHO
3
A 3 A A
CH2OH CH2OH CH2
glyceraldehyde dihydroxyacetone glyc
(an aldose) (a ketose)
Aldosas

ngage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electron
med that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserv
 fou
1
CH2OH CH2OH
2
A A
C PO CHOH
3 A A
CH2OH CH2OH
dihydroxyacetone glycerol
(a ketose)

Cetosas
e copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed
ally affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if
 aldo- or keto-forms we have depicted so far.
As an example, consider d-glucose. First, let us rewrite its Fischer projection for-
mula in a way that brings the OH group at C-5 within bonding distance of the carbo-
nyl group (as in eq. 9.14). This is shown in Figure 16.2. The Fischer projection is first

Reacción intramolecular converted to its three-dimensional (dash-wedge) structure, which is then turned on
its side and bent around so that C-1 and C-6 are close to one another. Finally, rota-
tion about the C-4!C-5 bond brings the hydroxyl oxygen at C-5 close enough for
nucleophilic addition to the carbonyl carbon (C-1). Reaction then leads to the cyclic,
hemiacetal structure shown at the bottom left of the figure.

1
CH P O CH P O
A
A OH
H OO
H #! OH
2
A
A 3
HO #! H H H HO H
A H
HO OO 6 % %4 % %2 1

O
OO
turn
A
A 4 908
HOH2C OO0 0 CH P O
05 0O
H #! OH 3
A OH
H OO 5 HO HO H OH
A
A H #! OH
H OO
A OH CH2OH
CH2OH 6
D-glucose D-glucose Allow C-1 and C-6 to
(Fischer projection) (dash-wedge structure) approach one another.

H OH
1 6 1
6 O C1 nucleophilic 6 HO CH P O rotate CH2OH CH P O
HOH2C H addition HOH2C H around H H
5 H HO 2 5 H HO 2 5 H HO 2
closes C-4–C-5
H OH the ring H OH bond HO OH
4 3 4 3 4 3
OH H OH H OH H
hemiacetal structure
of glucose

Figure 16.2
Manipulation of the Fischer projection formula of D-glucose to bring the C-5 hydroxyl group in position
for cyclization to the hemiacetal form.
 nyl group (as in eq. 9.14). This is shown in Figure 16.2. The
converted to its three-dimensional (dash-wedge) structure,
itscarbohydrate
The British side and bent around
chemist W. N.soHaworth
that C-1(Nobel
and C-6 are
Prize, close
1937) to on
introdu
a useful way oftion about the
representing theC-4!C-5
cyclic formsbond brings
of sugars. In the hydroxyl
a Haworth oxygen
projection,
Proyecciones de Haworth
nucleophilic
ring is represented
upper right. The carbons are
hemiacetal
addition
as if it were planartoand
arranged
structure
theviewed
carbonyl
clockwise
shown
edgecarbon
at thenumerically,
(C-1).
on, with
bottom leftwith
of the
Reaction
the oxygen
C-1figure.
at
at the ri
Substituents attached to the ring lie above or below the plane. For example,
Haworth formula for d-glucose (Figure 16.2) is written as
1
CH P O 6 CH P O6
A CH2OH CH2OH
A OH
H OO
H #! OH5
2
A
A
5
O 3 O H H
H HO #! H
A H
HO OO H 6 %

O
OO
turn
A
A 4 1 (H, OH) 44 HOH
908 1 (H, OH)
2 C 05 0
OH H H #! OH OH
A OH
H OO
HO 5 HO HO HO
A
A
3 2
H #! OH 3 2

H OO
A OH H OH CH2OH OH
CH2OH 6
Haworth projection formulas for D-glucose
D-glucose D-glucose
(Fischer projection)
Sometimes, as in the structure at (dash-wedge structure)
the right, the ring hydrogens are omitted so
attention can be focused on the hydroxyl groups.
In converting from one type of projection formula to another, notice that hydro
groupsOH
H on the right in the Fischer projection are down in the Haworth projection (
conversely, hydroxyl groups on the left in the Fischer projection
1 are up in the Hawo
6 O C 1
projection). For d-sugars, the terminal6 !CH
nucleophilic HOOH group CH upOin the Haworth
isP rotate pro
470
Proyecciones Haworth
Chapter 16 Carbohydrates

In practice, these forms are present to less than 1% in glucose solutions, but they a
important with other monosaccharides. The ketose d-fructose, for example, exi
in solution mainly in two furanose forms. The carbonyl carbon at C-2 and hydrox
group at C-5 cyclize to give the furanose ring.

6 1 6 1 6
HOCH2 O CH2OH HOCH2 OH CH2OH HOCH2 O OH anomeric
2
5 2 5 P 5 2 carbon (16
HO HO O HO
OH CH2OH
4 3 4 3 4 3 1
OH OH OH
D-fructose
(— OH at C-2 is “down”) (acyclic keto form)

PROBLEM 16.6 Draw Haworth projections of the a and b forms of

d-glucofuranose (eq. 16.4).

PROBLEM 16.7 d-Erythrose cannot exist in pyranose forms, but furanose cyclic
forms are possible. Explain. Draw the structure for a-d-erythrofuranose.
 carbon becomes chiral. Consequently, two hemiacetal structures are possible, depend
ing on the configuration at the new chiral center. The hemiacetal carbon, the carbon

Mutarrotación
acetal carbon in a cyclic that forms the new stereogenic center, is called the anomeric carbon. Two monosac
charide is the anomeric charides that differ only in configuration at the anomeric center are anomers (a spe
wo monosaccharides that
cial kind of epimers). Anomers are called a or b, depending on the position of the
configuration only at the
carbon are anomers. hydroxyl group. For monosaccharides in the d-series, the hydroxyl group is “down”
in the a anomer and “up” in the b anomer, when the structure is written in the usua
way (eq. 16.3).

anomeric
carbon
CH2OH CH2OH CH2OH
O OH O
H OH
PO (16.3
OH OH OH
HO OH HO HO

OH OH OH anomeric
D-glucose
carbon
(mp 1468C) (acyclic, aldehyde (mp 1508C)
form)

The a and b forms of d-glucose have identical configurations at every stereogenic cen-
ter except at C-1, the anomeric carbon.
How do we know that monosaccharides exist mainly as cyclic hemiacetals?
There is direct physical evidence. For example, if d-glucose is crystallized from
methanol, the pure a form is obtained. On the other hand, crystallization from ace-
Conformaciones Piranosas
16.7 Conformations of Pyranoses
Haworth projections depict pyranose rings as planar. However, as with cyclohexane,
the rings generally prefer a chair conformation (review Sec. 2.9). Consequently, we can
rewrite eq. 16.3 more accurately as eq. 16.6.
H
6
CH2OH H
4 OH
HO 5 2
HO 1
3 CH P O
H OH
H
D-glucose
(acyclic, aldehyde form) (16.6)

H H
6 6 b
CH2OH H CH2OH H
4 4
O O
HO HO
5 2 5 2
HO 1 H HO 1 OH
3 3
H OH H OH
a
H OH H H
Reacciones de los
MonoSacáridos
some of their commoncontain
Monosaccharides reactions.
hydroxyl groups. It is not surprising, then, that they undergo
reactions typical of alcohols. For example, they can be converted to esters by reac-
tion with acid halides or anhydrides. The conversion of b-d-glucose to its pentaacetate
16.8 Esters
by reaction andacetic
with excess Ethers from
anhydride Monosaccharides
is typical; all five hydroxyl groups, including

reactions Ésteres y Éteres

the hydroxyl at the anomeric C-1, are esterified. (To clarify the structure, the ring H’s
Monosaccharides contain hydroxyl groups. It is not surprising, then, that they undergo
are omitted.)
typical of alcohols. For example, they can be converted to esters by reac-
tion with acid halides or anhydrides. The conversion of b-d-glucose to its pentaacetate 6
CH2OH
by reaction with excess
A
acetic anhydride is typical; all five hydroxyl groups, includingCH2OAc
the hydroxyl at the anomeric C-1, O O
O are esterified. (To clarify A O
B Bthe structure, the 4ring H’s
HO
are omitted.) A CH3COCCH3 AcO 2A 5
HO OH pyridine, 0ºC 6 AcO OA
1
CH2OH CH2OAc
A A O A O O A OA 3 A
HO
OH B B
AcO 4 OAc
A CH3COCCH3 2A
5
HO pyridine, 0ºC AcO OAc (16.7)
OH 1
The hydroxyl groups A A
OHcan also be converted to ethers by treatment with
OAc an alkyl
A A3 O
B
halide and a base (the Williamson synthesis, Sec. 8.5). Because sugars are sensitive to Ac 5 CH3CO
strong bases, the mild base silver oxide is preferred.
The hydroxyl groups can also be converted to ethers by treatment with an alkyl
halide and a base (the Williamson synthesis, Sec. 8.5). Because sugars are
6 sensitive to
strong bases, CH OH CH2OCH3
A the mild2base silver oxide is preferred.
O A O
5
HO CH2OH A Ag2OCH3O CH OCH 6 4
2A
2 3
A O CH3I
A O (16.8)
HO HO CH3O 4 CH35O 3 1
A Ag2O 2A

A
A

A A
HO OHCH3I CH3O
3 1 H3CO (16.8)

A
A

A A
OH OH H3CO OCH3
OH OCH3

Copyright 2010 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook
 manipulation with organic reagents.

16.9
Reducción
Reduction of Monosaccharides
The carbonyl group of aldoses and ketoses can be reduced by various reagents. The
carbonyl group of an products are polyols, called alditols. For example, catalytic hydrogenation or reduc-
etose is reduced, tion with sodium borohydride (NaBH4) converts d-glucose to d-glucitol (also called
t is an alditol, an
sorbitol; review Sec. 9.12).
yol.

CH P O CH2OH
CH2OH H OO OH H OO OH
A HO OO H
O HO OO H H2, catalyst
HO A H OO OH or NaBH4 H OO OH (16.9)
A
HO OH H OO OH H OO OH
A A
OH CH2OH CH2OH
D-glucose D-glucose D-glucitol
(cyclic) (acyclic) (sorbitol)

Reaction occurs by reduction of the small amount of aldehyde in equilibrium with the
cyclic hemiacetal. As that aldehyde is reduced, the equilibrium shifts to the right, so
that eventually all of the sugar is converted. Sorbitol is used commercially as a sweet-
ener and sugar substitute.

aldehyde group of an PROBLEM 16.9 d-Mannitol, which occurs naturally in olives, onions,
Alditoles
 16.10 Oxidation16.11
of Monosaccharides
Formation of Glycosides from Monosaccha

equilibrium
the
nd thegroups
hyde
oxidizing
primarycanalcohol
be
agents,
with a small
blue solution gives but
group,
1 easily
Oxidación
Although aldoses exist primarily in cyclic hemiacetal forms, these structures are in
Stronger such
finite
a red asamount
aqueous
precipitate
producing
oxidized
21 to acids
ofnitric
of
dicarboxylic
(review
acid,oxide,
oxidize
the open-chain
cuprous
acids
Sec.
Cuthe
called
9.13). The
2
aldehyde
aldehyde.
O. A Thesegroup
alde-
carbohydrat
aldaric acids.
products are ofFor
called
reacts with Ag or Cu is called a reducing sugar because reduction the
xample,
aldonic d-glucose
acids. For gives d-glucaric
example, acid.is easily oxidized to d-gluconic acid.
d-glucose
accompanies oxidation of the aldehyde group. These reagents are used in labor
tests for this property.
CHPPOO
CH COOH
COOH
HHOOOOOH OH H OO
HOOO OHOH
HO
HOOO OOHH Br2, H32O HOHO
HNO BOO H H
OO (16.12)
(16.10)
21
RCH P O 1 2 Cu
HHOOOO1OH5 OH 1
OH
2 or
21 RCO
H H
OO
2
1OH
OH
OO Cu2O 1 3 H2O (
Ag or Cu
blue
HHOOOOOH OH OHOHred
H OO
H OO
solution precipitate
CHCHOH
2 2OH CH
COOH2OH
D-glucose
D-glucose D-gluconic
D-glucaric acidacid

PROBLEM
The Reactivos
oxidation 16.10 Write
of aldoses de:equation
an
is so easy that they for
reactthe reaction
with of oxidizing
such mild d-mannose wit
agents
21
Fehling’s
as Tollens’ reagent
reagent (Ag 1
(Cu
Tollens
in ) to
–
aqueousgive
Plata d-mannonic
ammonia),
PROBLEM 16.11 Write the structure of d-mannaric acid.
Fehling’s reagent
acid. (Cu 21
complexed
21
with tartrate ion), or Fehling
Benedict’s reagent (Cu complexed with citrate ion). With
– Cobre con tartrato
Tollens’ reagent, they give a silver mirror test (Sec. 9.13), and with the copper reagents,
Benedict – Cobre con citrato
Stronger oxidizing agents, such as aqueous nitric acid, oxidize the aldehyde
Ácidos y Lactonas
Amino Azúcares
Enlace Glucosídico
 b-d-galactose with methanol.

Enlace Glucosídico
The mechanism of glycoside formation is the same as that described in eq. 9.13 of
Section 9.7. The acid catalyst can protonate any of the six oxygen atoms, since each has
unshared electron pairs and is basic. However, only protonation of the hydroxyl oxygen
at C-1 leads, after water loss, to a resonance-stabilized carbocation. In the final step,
methanol can attack from either “face” of the six-membered ring, to give either the
b-glycoside as shown or the a-glycoside.

CH2OH HOCH2 H HOCH2

O O 1
O
OH OOH
H1 2H2O 1
1 H
OH OH OH
HO HO HO

OH OH OH
(16.14)

HOCH2 HOCH2 H HOCH2 1

H
O O 1 O OCH3
OCH3 1 OCH3
2H CH3OH
H
OH H OH OH
HO HO HO

OH OH OH

Naturally occurring alcohols or phenols often occur in cells combined as a glyco-

Disacáridos
 ccharides are disaccharides. In a disaccharide, two mono- A disaccharide consists of two
the C-4 hydroxyl group of the unit
glycosidic bond between the anomeric carbon of one mono- at the right as an linked
monosaccharides acetalby (glycoside).
a The configura-
tion atunit.
the In
anomeric carbon
we willof the left unit is a.bond
glycosidic In between
the crystalline
the form, the anomeric
Maltosa
xyl group on the other this section, describe
anomeric carbon of one unit and
carbon
of four important of the right unit has the b configuration.
disaccharides. a hydroxyl groupBoth units
on the other are pyranoses, and the
unit.
right-hand unit fills the same role as the methanol in eq. 16.13.

CH2OH CH2OH H
obtained by the partial hydrolysis of starch. Further hydro- Some common disaccharides are
O therefore, consist of two O maltose, cellobiose, lactose, and CH2OH
-glucose (eq. 16.2). Maltose must,
H H OH H
ns out that the anomeric carbon of the left unit is linked to sucrose. O
he unit at the right as an 19 4 q HO
OHacetal (glycoside). The configura-
OH a
HO
n of the left unit is a. In the crystalline form, the anomeric HO 29 19
H
O
s the b configuration. Both units are pyranoses, and the H
6
a b H OH C
me role as the methanol in eq. 16.13.
OH OH 4
Hidrólisis parcial
H del almidón O
CH2OH H
O CH2OH H
Tollens = positivo acetal HO
OH (glycosidic)
q HO
O Mutarotación = positivo
carbon
OH a
HO 29 19
H 6
H
H CH2OH H
b H OH
OH 4
O b
H O 5
The systematic nameacetal for maltose,
HO shown 2beneath the OHcommon name, describes
the structure fully, including the name of3 Heach unit
(glycosidic)
OH(d-glucose), the ring sizes (pyra-
1
carbon
nose), the configuration at each anomeric H carbon (a
H or b), and the location of the
hydroxyl group involved in the glycosidic link (4-O).
4-O-(𝛼-D-Glucopiranosil)-𝛽-D-Glucopiranosa
or maltose, shown beneath the common name, describes
g the name of each unit (d-glucose), the ring sizes (pyra-
each anomeric carbon (a or b), and the location of the
 hydrolysis
The anomeric carbon of the right glucose unit inof cellobiose
maltose gives only
is a hemiacetal. Natu- d-glucose. Cellobiose m
of maltose.
rally, when maltose is in solution, this hemiacetal will becellobiose
In fact,
function differs
in equilibrium with from maltose only in h
the open-chain aldehyde form. Maltose, therefore,
C-1 of the gives a positiveunit.
left glucose Tollens’ test and
Otherwise, all other structural f
Celobiosa
other reactions similar to those of the anomeric carbon in glucose.
ing a link from C-1 of the left unit to the hydroxyl group a
PROBLEM 16.13 When crystalline maltose is dissolved in water, the initial
CH2OH
specific rotation changes and gradually reaches an equilibrium value. Explain.
O b H
CH2OH H OH
CH2OH H
O
16.12.b Cellobiose 4 1
O b
O OH q of cellulose. Further
Cellobiose is the disaccharide obtained by the partial hydrolysisHO HO
hydrolysisOHof cellobiose19gives only d-glucose.
3 Cellobiose
2 mustHidrólisis
thereforeHObe an parcial
isomer de29 celulosa O
29
HO
of maltose. In fact, H
cellobiose differs from maltose only in having the b configuration at
b all other OH Tollens = positivo
includ-H
19 4
C-1 of the left glucose unit. Otherwise, structural features are identical, OH HO
ing a link from C-1 of the left unit to the hydroxyl group at C-4 in the right unit.
OH MutarotaciónH = positivo H H
CH2OH
b
O b H H H
H OH
CH2OH H H OH
1 b 3
4
OH O
O q HO Note that,HOin the conformational
5
2 1 OHformula for cellobiose, o
19
H
3 2 HO the
29 “rear”O and one to the
O “front” of the molecule. This is t
OH 19 4
H cellulose chain.
b H
OH HOCH2
6
H H H H
alen Rowell/CORBIS

16.12.c Lactose
4-O-(𝛽-D-Glucopiranosil)-𝛽-D-Glucopiranosa
Note that, in the conformational formula for cellobiose, one ring oxygen is drawn to
LactoseThis
the “rear” and one to the “front” of the molecule. is the major
is the way thesugar in human
rings exist in the and cow’s milk (4% t
cellulose chain.
 H OH equimolar
lactose gives H of d-galactose and d-glucose. Th
HOCHamounts
2

© Gal
6
H unit
H of the galactose H has the b configuration at C-1 and is linked to

Lactosa
Cheese whey is a source of lactose, at C-4 of the glucose unit. The crystalline anomer, with the a conf
also known as milk sugar. cose unit, is made commercially from cheese whey.
Note that, in the conformational formula for cellobiose, one ring oxygen is drawn to
6
the “rear” and one to the “front” ofCHthe2OH
molecule. This is the wayOH
the rings exist in the
cellulose chain. 5 a
b O CH2OH H H
CH2OH H b
© Galen Rowell/CORBIS

O 6
CH2O
16.12.c O H
HO Lactose
4 1
OH
19 O 3 2 OH q HO O 4
Lactose is the major sugar in human and cow’s milk (4% to 8% lactose). Hydrolysis of 29 5
OH
lactose gives equimolar amounts of d-galactose and d-glucose. The H
anomeric carbon OH
19
HO
29 H OHat C-1 and is linked
of the galactose unit has the b configuration 4% humana
to the hydroxyl
H /group
8% vacaH
3
H
at C-4 of the glucose unit. The crystalline anomer, with the a configuration at the glu-
actose, OH glucose unit
cose unit, is made commercially from cheese whey.
Tollens = positivo H
galactose unit Queso / yogurt
6
CH2OH OH
5 a
b O CH2OH H H
H b
O 6
CH2OH H
4 1 H
OH O
19 O 3 2 OH q HO O 4
29 5
19
H H OH HO 2 1 H
OH Copyright 2010 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in 3
H Cengage Learning
Hoverall learning experience.
H does not materially affect the
Editorial review has deemed that any suppressed content OHreserves the right to remove additional content at any time
whole or in part. Due to electronic rights, some third party content may be suppresse

glucose unit H OH
a

25566_16_ch16_p460-491.indd 476
4-O-(𝛽-D-Galactopiranosil)-𝛼-D-Glucopiranosa
478 Chapter 16 Carbohydrates

Sacarosa
linked via oxygen to C-2 of the fructose unit. An additional difference is tha
tose unit is in the furanose form.
478 Azúcar de mesa
Chapter 16 Carbohydrates
6
CH2OH Mutarotación = negativo
5 linked via oxygen to C-2 of the fructose unit. An additional difference is that the fruc-
O Tollens
tose unit is in the furanose = negativo
form.
D-glucose 4 1 Azúcar no reductor H
CHOH
6
unit OH 2 6
HO 5
O 2 Azúcar invertidoCH=2OH Sacarosa
H hidrolizada
3 O
4 5 H
D-glucose 4
OH OH
1 HHO
unit 6 2 OH
HO 2 CHHO
2OH H 1 H
3 O q4 O3
OHH 4
5
OH HO H OH
HO
2
H
OH H 3
6
OO q H
1
O O 5
D-fructose HOH2C 3
H 4
OH
H 3
a 2OH 6
unit 5 2 O
HOH2C
6
O HO H O b
1
5 CH2OH
D-fructose
unit 5 2
CH2OH a 2
CH2OH H
4 HO
1 b
3 1
CH2OH CH2OH H
4 OH
3
1

OH

(𝛼-D-Glucopiranosil)-𝛽-D-Fructofuranosa
• Sacarina
Edulcorantes
• Aspartame
• Sucralosa
• Ciclamato
• Estevia
• Neotame
• Ace-Sulfamato de potasio
• Neohesperidina dihidrocalcona
• Sorbitol
Sacarina
Aspartame
Sucralosa
Ciclamato
Estevia
Neotame
Ace-Sulfamato de potasio
Neohesperidina dihidrocalcona
Sorbitol
 Polisacáridos

• Almidón y Glucógeno
• Celulosa
• Quitina
• Almacenamiento y estructura
 Almidón

• Cereales, papas, maíz y arroz - Plantas

• Almidón = Amilosa 20% + amilopectina 80%
• Enlaces: 1,4, 𝛼 Glucosídicos (lineales)
• Enlaces: 1,6, 𝛼 Glucosídicos (ramificados)
 Glycogen is the energy-storing carbohydrate of animals. Like starch, it is made of
1,4- and 1,6-linked glucose units. Glycogen has a higher molecular weight than starch
(perhaps 100,000 glucose units), and its structure is even more branched than that of

Amilosa
amylopectin, with a branch every 8 to 12 glucose units. Glycogen is produced from
glucose that is absorbed from the intestines into the blood; transported to the liver,
muscles, and elsewhere; and then polymerized enzymatically. Glycogen helps maintain
the glucose balance in the body by removing and storing excess glucose from ingested
food and later supplying it to the blood when various cells need it for energy.

maltose unit
CH2OH H
4
O
O
HO 1 H H
OH CH2OH H
H 4
O
H O
HO 1 H
H OH H CH2OH H
4
O
H a
O
HO 1 H H
OH CH2OH H
H 4
O
H a O
HO 1 H
H OH

amylose H O
n

Figure 16.5
Structure of the amylose fraction of starch.

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 16.13 Polysaccharides

Amilopectina
H
CH2OH H
4
O
O
HO H
H OH 1 H CH2OH H
O
H O 4

HO H
H
H OH 1
CH2OH H
4
O H 1,6-link
O (a branch point) 1,6 bra
H C-4 en
HO O
OH 1 H CH2OH H C-1 en
H
O
H O 4
1,4-link 6
HO H CH2
H OH 1 H H
O
H O 4

HO 1 H
H OH
amylopectin H O
Figure 16.6
 Glucógeno

• Reserva energía en los animales

• Enlaces: 1,4 y 1,6, 𝛼 Glucosídicos
• Más grande que almidón
• Más ramificada que Amilopectina (cada 8 a 12)
 Glucógeno

• Desde intestinos a la sangre

• Transportado: a Hígado y músculos
• Polimeriza enzimáticamente
• Mantiene el equilibrio de glucosa en sangre
Celulosa
 fibrils bound together by hydrogen bonds between hydroxyls on adjacent chains. Cellu- in cellulose nitrate, they are
lose fibers having considerable physical strength are built up from these fibrils, wound nitrated. Guncotton, a highly

Celulosa
spirally in opposite directions around a central axis. Wood, cotton, hemp, linen, straw, nitrated cellulose, is an explosive.
and corncobs are mainly cellulose.

cellobiose unit

H 6 H 6
H H CH H H CH
2OH 2OH
H OH H b H OH H
1 4 1 4
O O
HO O HO O
O 4
HO 1 O 4
HO O
O O
CH2OH H H OH CH2OH H b H OH
6 6
H H H H H H
n
cellulose chain

• Lineal = Enlaces 1,4,𝛽 Glucosídicos

Figure 16.7
Partial structure of a cellulose molecule showing the b linkages of each glucose unit.

• > 5000 unidades de glucosa + ….

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• Puentes de hidrógeno entre cadenas adyacentes

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6_ch16_p460-491.indd 481 10/18/10 6:13

• Madera, algodón, cáñamo, lino, paja y mazorcas de

maíz – Estructuras de sostén
 Celulosa

• No podemos digerir celulosa

• ¿porqué? = esteroquímica del enlace glucosídico.
• 𝛼-glucosídico = Si y los 𝛽-glucosídicos = No
• Vacas, polillas .. Rumiantes.
 16.13 Polysaccharides 483
O
6 B O
H CH2OCCH H H

Celulosa
(cellulose) as their main food.3 Ruminants (cud-chewing animals B such as cows) can
digest grasses and H O CH CO
theyHharbor3 the necessary
4 other forms of cellulose because B 1 microor-
ganisms inOtheir rumen. O
CH3CO O
Cellulose is the raw material for several commercially important derivatives. Each
CH3CO
glucose unit in 1 O 4
B cellulose contains three hydroxyl groups. These hydroxylO groups can be
modified by O H CH3that
the usual reagents CO react with alcohols. For H example, cellulose reacts
Tres grupos hidroxilo reactivos … ¿reaccionan?
H
B
with acetic anhydride to give cellulose H
O
acetate.
H CH2OCCH3
6 B
O O
6 Bsegment of a cellulose acetate molecule O
H CH2OCCH H B H
Cellulose with4 about 97% of
3
H the hydroxyl O groupsH acetylated
CH3CO is used to make Acetato de celulosa
O B 1
acetate rayon.
O CH3CO O Películas fotográficas
Cellulose nitrate is another useful cellulose derivative. Like glycerol, cellulose
CH3CO with nitric acid to a 1nitrate
can be converted
B
O 4 ester (compare eq. 7.41). The number
O Hilos - Textil
of hydroxyl groups
O H CH
nitrated per3CO
glucose unit determines the Hproperties of the prod-
B
uct. Guncotton, a highly nitrated cellulose, is an efficient explosive used in smokeless
H O H H CH2OCCH3
powders. 6 B
O
6 segment of a cellulose acetate molecule
H CH2ONO2 H H
Cellulose with4 about 97% H of the hydroxyl groupsHacetylatedO2NO is used to make Nitrato de celulosa
1
O
acetate rayon. O
O2NO O Explosivos
Cellulose nitrate is another useful cellulose derivative. Like glycerol, cellulose
O2NO with nitric acid to a 1nitrate
can be converted O 4 ester (compare eq. 7.41). The number
O Pinturas, lacas, tintas
H
of hydroxyl groups nitrated per
O2NOglucose unit determines theH properties of the prod-
uct. Guncotton, a highly nitrated cellulose, is an efficient explosive used in smokeless
H H H CH 2ONO 2
powders. 6
segment of a cellulose nitrate molecule
6
H CH2ONO2 H H
 Quitina
• Polisacárido que contiene nitrógeno.
• Similar a la celulosa.
• Cambio en C-2 OH por grupo acetilamino.
 Quitina - Quitosano
• Glucosa es a celulosa
• N-acetilglucosamina (N-acetil-D-Glucos-2-amina) es a quitina.
• Quitina – acetilo = quitosano (soluble acidos inorgánicos)
• Medicina, fungicida, crecimiento plantas, quesos light…
 Esteres Fosfato
16.16 Amino Sugars

16.14 Sugar Phosphates

Phosphate esters of monosaccharides are found in all living cells, where they are interme-
diates in carbohydrate metabolism. Some common sugar phosphates are the following:
6
CH2OPO322
1CH P O 5
CH2OH O 5
H H 22
O3POH2C O OH
2 A
H OO OH CPO 4 1 4 1
A OH H H H
3 H H
CH2OPO322 CH2OPO322 HO OH
3 2
3 2
D -glyceraldehyde- dihydroxyacetone
3-phosphate phosphate H OH OH OH
a -D -glucose- b -D -ribose-5-phosphate
6-phosphate

Phosphates of the five-carbon sugar ribose and its 2-deoxy analog are important in nu-
cleic acid structures (DNA and RNA) and in other key biological compounds (Sec. 18.12).

• En las células
16.15 Deoxy Sugars
con vida.
• Intermedios de metabolismo.
In deoxy sugars, one or more of the hydroxyl groups is replaced by a hydrogen atom.
The most important example is 2-deoxyribose, the sugar component of DNA. It lacks
In deoxy sugars, one or mor
the hydroxyl groups of the p

• C5 ribosa …. DNA y RNA.

the hydroxyl group at C-2 and occurs in DNA in the furanose form.
5
O CH P O
carbohydrate is replaced by
hydrogen atom.

HOH2C OH

O O
4
H
1 q CH2
H 3 2 H H OO OH
no OH group H OO OH
OH here
CH2OH
b -D-deoxyribofuranose
16.15 Deoxy Sugars

Desoxi azúcares
n deoxy sugars, one or more of the hydroxyl groups is replaced by a hydrogen ato
he most important example is 2-deoxyribose, the sugar component of DNA. It la
he hydroxyl group at C-2 and occurs in DNA in the furanose form.
5
O CH P O
HOH2C OH

O O
4
H
1 q CH2
H 3 2 H H OO OH
no OH group H OO OH
OH here
CH2OH
b -D-deoxyribofuranose
(the sugar of DNA)

• Uno o mas “OH” reemplazado por “H”

16.16 Amino Sugars
• DNA
n amino sugars, one of the sugar hydroxyl groups is replaced by an amino gro
sually the —NH2 group is also acetylated. d-Glucosamine is one of the more abu
 (vitamin C)
[mp 1928C (decomposes)]
16.17 Ascorbic Acid (Vitamin
pleasant, sharp-acid taste
C)

Asl-AscorbicVitamina C – Ac. Ascórbico

a consequence
eral unusual
roascorbic
acid (vitamin
features.
acid.
C) resembles
of this structural
The compound
Both forms
a monosaccharide,
feature, ascorbic acid isbut
has a five-membered
are biologically
its structure
easily oxidized has sev-
to dehy
unsaturated lactone ring
effective as a vitamin.
(review
ThereSec.
is no10.12) with two
carboxyl group hydroxyl groups
in ascorbic attached
acid, but ittoisthe doubly bonded
nevertheless carbons.
an acid with a
KThis
of enediol
4.17. The structure
proton is
of relatively
the uncommon.
hydroxyl group at C-3 is acidic, because the anion tha
a
esults from its loss is resonance
6 stabilized and similar to a carboxylate anion.
CH2OH CH2OH
CH2OH H OO OH CH 2OHOH

O
O
5 H OO
H OH
L configuration O H OH O
O
at this stereogenic 1 air O
center 4 P O oxidation PO
2
H O H O
3 2
H H

P
HO OH O O
O proton OH L-ascorbic acid
acidic OH acid
Odehydroascorbic
2
(vitamin C)
[mp resonance stabilized ascorbate anion
1928C (decomposes)]
pleasant, sharp-acid taste
Humans, monkeys, guinea pigs, and a few other vertebrates lack an enzyme tha
Transporte – Gram Positivo
Transporte – Gram Negativo
 Transporte - Sangre
léculas: carbohidratos

Tabla 25.1 Compatibilidades de los grupos sanguíneos humanos

Tipo sanguíneo del receptor
Tipo sanguíneo del donador A B AB O

A o x o x
B x o o x
AB x x o x
O o o o o
 propios marcadores únicos, o determinantes antigénicos; las células del tipo AB tie-
nen marcadores del tipo A y del tipo B. En la figura 25.12 se muestran las estruc-
turas de los determinantes de los tres grupos sanguíneos. Nótese que los

Transporte - Sangre
constituyentes monosacáridos de cada marcador están entre los ocho azúcares
esenciales mostrados anteriormente en la figura 25.9.

Grupo sanguíneo A enlace enlace N-acetil-D-

L-fucosa D-galactosa Proteína
1 2 1 4 glucosamina

enlace 1 3

N-acetil-D-
galactosamina

Grupo sanguíneo B enlace enlace N-acetil-D-

L-fucosa D-galactosa Proteína
1 2 1 4 glucosamina

enlace 1 3

D-galactosa

Grupo sanguíneo O enlace enlace N-acetil-D-

L-fucosa D-galactosa Proteína
1 2 1 4 glucosamina

Figura 25.12 Estructuras de los determinantes antigénicos de los grupos sanguíneos A,

B y O.