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CHAPTE2R 28

CHEMISTRY OF THE LIVING STATE


PRACTICE EXAMPLES
1A

(E)
H 2N

O
CH

NH

CH

C H OH

CH O H

CH3

CH 3

O
NH

CH

OH

(CH2 ) 2
S

CH3

The amino acids are threonine, threonine, and methionine. This tripeptide is
dithreonylmethionine.
1B

(E) The amino acids are serine, glycine, and valine. The N terminus is first.

H2N CH C NH CH
CH2
OH

C NH

CH

H3C

CH

OH

CH3

2A

(M) Because it is a pentapeptide and five amino acids have been identified, no amino acid is
repeated. The sequences fall into place, as follows.
Gly Cys
second fragment
Cys Val Phe
third fragment
Val Phe
first fragment
Phe Tyr
fourth fragment
pentapeptide sequence Gly Cys Val Phe Tyr

2B

(M) Because it is a hexapeptide and there are five distinct amino acids, one amino acid must
appear twice. The fragmentation pattern indicates that the doubled amino acid is glycine.
The sequences fall into place if we begin with the N-terminal end.
Ser Gly Gly
third fragment
Gly Gly Ala
second fragment
Ala Val Trp fourth fragment
Val Trp first fragment
hexapeptide sequence Ser Gly Gly Ala Val Trp

1303

Chapter 28: Chemistry of the Living State

INTEGRATIVE EXAMPLE
A.

(M)
MRT
mol MyG 0.500 g MyG
M

1 mol MyG
2.985 105 mol MyG
16900 g MyG

2.985 105 mol MyG


0.0011834 M
0.025 L

0.0011834 M 0.08206 L atm K 1 298 K 0.02894 atm


101325 Pa
2932 Pa
1 atm
To determine the height of the water column, several things should be kept in mind:
(Pa) 0.02894 atm

1) The pressure unit, 1 Pascal (Pa) is defined as 1 N/m2 (1 Newton of force per m2)
2) Force (F) in Newtons is given by F = mg. Since m is in units of kg and g in units of m/s2,
Newtons can be expressed in units of kgm/s2.
With the above points in mind,
F mg
P
A
A
Since mass (m) = density (D) volume (V), we can make the following substitutions:
m g D V g D w l h g

D hg
A
A
wl
N
kg
m
2932 2 1000 3 h 9.8 2
m
m
s
h 0.300 m
P

1304

Chapter 28: Chemistry of the Living State

(D)
(a)
O

OH

OH

H
H2O
O

OH
C

+
(b)

Given
Data
Rate
(M/s), V
9.02E-05
1.67E-04
2.90E-04
6.47E-04

[CO2]
(M), S
1.25E-03
2.50E-03
5.00E-03
2.00E-02

1.2E+04

Lineweaver-Burk Eq.
1/V
1/S
1.11E+04
5.99E+03
3.45E+03
1.55E+03

8.00E+02
4.00E+02
2.00E+02
5.00E+01

y = 12.72281x + 905.07396
R2 = 1.00000

1.0E+04
8.0E+03

1/V

B.

6.0E+03
4.0E+03
2.0E+03
0.0E+00
0

100

200

300

400

500

1/S

1305

600

700

800

900

Chapter 28: Chemistry of the Living State

The Lineweaver-Burk equation is


K
1
1
1

M
V Vmax Vmax S
From the graph and the linear regression, we can see that the slope of the line m (KM/Vmax) =
12.7228 s, and the y-intercept b (1/Vmax) = 905.074 (M/s)-1. Therefore,
Vmax = 1/905.074 = 0.001105 M/s

KM
KM

12.723 s
Vmax 0.001105 M/s
K M 0.01406 M=14.1 mM
From the problem, we note that Vmax k 2 E 0 . The value for k2, therefore, is:
k2

Vmax 0.001105 M/s

4.8 105 s 1
9

E
2.3
10
M
0

EXERCISES
Structure and Composition of the Cell
1.

(M) The volume of a cylinder is given by V = r 2 h = d 2 h / 4 .


2
1000 L
V = 3.14159 1 106 m 2 106 m 4
= 1.6 1015 L
3

1m
The volume of the solution in the cell is Vsoln = 0.80 1.6 1015 L = 1.3 1015 L .

(a)

H + = 106.4 = 4 107 M

4 107 mol H + ions 6.022 1023 ions


no. H 3O ions = 1.3 10 L

1 L soln
1 mol ions
2
+
= 3 10 H 3O ions
+

(b)

2.

15

1.5 104 mol K + ions 6.022 1023 ions

1 L soln
1 mol ions
+
5
+
no. K ions = 1.2 10 K ions
no. K + ions = 1.3 1015 L

(E) Mass of all lipid molecules = 0.02 2 1012 g = 4 1014 g.


1u
1 lipid molecule
lipid molecules = 4 1014 g
= 3 107 lipid molecules

24
1.66 10 g
700 u

1306

Chapter 28: Chemistry of the Living State

3.

(E) mass of protein in cytoplasm = 0.15 0.90 2 1012 g = 2.7 1013 g.

no. of protein molecules = 2.7 1013 g

1 mol protein 6.022 1023 molecules

3 104 g
1 mol protein

= 5 106 protein molecules


4.

(M)
450 pm
1012 m
DNA length = 4.5 10 mononucleotides
= 2 103 m = 2 mm

1 mononucleotide 1 pm
3
2 mm = 2 10 m . Thus the length of the stretched out DNA is one thousand times the
length of the cell, which is 2 m . Consequently, the DNA must be wrapped up, or coiled,
within the cell.
6

Lipids
5.

6.

(M)
(a) C15 H 31COOH is palmitic acid. C17 H 29 COOH is linolenic acid or eleosteric acid.
C11H 23COOH is lauric acid. Thus, the given compound is glyceryl
palmitolinolenolaurate or glyceryl palmitoeleosterolaurate.
(b)

C17 H 33COOH is oleic acid. Thus, the compound is glyceryl trioleate or triolein.

(c)

C13 H 27 COOH is myristic acid. Thus, the compound is sodium myristate.

(E)
(a)

glyceryl palmitolauroeleosterate
O
CH2O

(CH2)14CH3

O
CHO

(CH2)10CH3

O
CH2O

(b)

(CH2)7 CH

CH

tripalmitin
O
CH2O

(CH2)14CH3

O
CHO

(CH2)14CH3

O
CH2O

(CH2)14CH3
1307

CH CH

CH

CH(CH2)3CH3

Chapter 28: Chemistry of the Living State

(c)

potassium myristate
O

CH3(CH2)12

C O K

(d) butyl oleate


O
CH3(CH2)3

7.

O C

(CH2)7 CH

CH

(CH2)7 CH3

(M)
(a)
Trilaurin
O

CH2 O C
O

(b)

C11H23

Trilinolein
O

CH2 O C
O

C17H31

CH O C C11H23
O

CH O C C17H31
O

CH2 O C C11H23
A triglyceride or glycerol ester

CH2 O C C17H31
A triglyceride or glycerol ester

Saturated triglyceride
-made using saturated acid

Unsaturated triglyceride
-made using unsaturated acid

A fat (usually solid at room


temperature)

An oil (usually liquid at room


temperature)

Soaps: salts of fatty acids (from saponification of triglycerides)


Phospholipids: derived from glycerols, fatty acids, phosphoric acid, and a nitrogen
containing base (both soaps and phospholipids have hydrophilic heads and
hydrophobic tails.)

1308

Chapter 28: Chemistry of the Living State

8.

(M)
O
CH2 O

O
CH2

C
O
C

R'
HO

OH

R'

C
O

CH2 O

OCH2CH2NH3

H C

HOC

O
CH2

CH
2
H
C

2
NH

C
O

O
O

H2 CH

2 N(CH
3 )2

CH2 O

C
O

R'

C
O

CH2 O

OCH2CH2NH(CH3)2

H C

OH

Monoglyceride

Diglyceride

OH
HO
R
CH2 C CH2
O C
H
O

R
OH
O C H2C
R
O C CH2
O C
H
O

9.

(E) Polyunsaturated fatty acids are characterized by a large number of C = C double bonds
in their hydrocarbon chain. Stearic acid has no C = C double bonds and therefore is not
unsaturated, let alone polyunsaturated. But eleostearic acid has three C = C double bonds
and thus is polyunsaturated. Polyunsaturated fatty acids are recommended in dietary
programs since saturated fats are linked to a high incidence of heart disease. Of the lipids
listed in Table 27-2, safflower oil has the highest percentage of unsaturated fatty acids,
predominately linoleic acid, which is an unsaturated fatty acid with two C=C bonds.

10.

(E) Safflower oil contains a larger percentage of the unsaturated fatty acid, linoleic acid
(two C=C bonds) (75 80%), than does corn oil (34 62%). It also contains a smaller
percentage of saturated fatty acids, particularly palmitic acid (6 7%) than does corn oil
(8 12%). And the two oils contain about the same proportion of the unsaturated fatty acid,
oleic acid (one C=C bond). Consequently, safflower oil should require the greater amount of
H2(g) for its complete hydrogenation to a solid fat.

1309

Chapter 28: Chemistry of the Living State

11.

(E)

tripalmitin

saponification products of tripalmitin:


sodium palmitate and glycerol

C H 2 OOC CH 2 14 CH 3
|
CHOOC CH 2 14 CH 3
|
C H 2 OOC CH 2 14 CH 3

12.

CH 2 OHCHOHCH 2 OH
NaOOC CH 2 14 CH 3

(E) First we write the equation for the saponification reaction.

C H 2 OOCC13 H 27
|
CHOOCC13 H 27 + 3 NaOH CH 2OHCHOHCH 2 OH + 3 NaOOCC13 H 27
|
C H 2 OOCC13 H 27
mass of soap = 105 g triglyceride

1 mol triglyceride
3 mol soap
250.4 g soap

723.2 g triglyceride 1 mol triglyceride 1 mol soap

= 109 g soap

Carbohydrates
13.

(M)

C
(S)

HO C

H
CH2OH

(S)

H C OH
(R)

(S)

HO C
HO C

C O
(R)

H C OH
CH2OH

CH2OH

D-Erythrulose
Ketotetrose

L-Glucose
Aldohexose

1310

Chapter 28: Chemistry of the Living State

14.

(M)

CHO

CHO

OH

HO

OH

HO

HO

OH

H
CH2OH

D-Glucose
15.

OH

HO

CH2OH

L-Glucose

These molecules are enantiomers

(M)
(a) D-( )-arabinose is the optical isomer of L-( + )-arabinose. Its structure is shown
below.
(b)

A diastereomer of L-( + )-arabinose is a molecule that is its optical isomer, but not its
mirror image. There are several such diastereomers, some of which are shown below.
(a)

H C

(b)
O

OH HO

OH HO

OH HO

H C

OH

OH HO

H HO

OH H

OH HO

H C

OH

OH HO

OH HO

H HO

OH

HO

CH2OH

16.

The designation L in L-Glucose simply arises


from nomenclature and does not convey either a
dextrorotatory or levorotatory designation. The
structure of a chiral molecule will determine
whether it is dextrorotatory or levorotatory. Put
another way, the D- and L- designation arises
from the rules of nomenclature, whereas the
dextrorotatory or levorotatory designation must
be experimentally determined.

CH2OH

CH2OH

CH2OH

CH2OH

CH2OH

CH2OH

(M)
H

OH

H2C

HO

O
H
H

HO

OH

OH
H

equitorial at C1
(a) has OH equatorial

OH

OH

HO

OH

OH

CH2OH

(c) H

OH

All three molecules


are optically active
cyclized/open-chain forms

1311

O
C

HO

(b)

CH2OH

Chapter 28: Chemistry of the Living State

17.

18.

19.

(M)
(a) A dextrorotatory compound rotates the plane of polarized light to the right, namely
clockwise.
(b)

A levorotatory compound is one that rotates the plane of polarized light to the left,
namely counterclockwise.

(c)

A racemic mixture has equal amounts of an optically active compound and its
enantiomer. Since these two compounds rotate polarized light by the same amount but
in opposite directions, such a mixture does not exhibit a net rotation of the plane of
polarized light.

(d)

(R) In organic nomenclature, this designation is given to a chiral carbon atom. First,
we must assign priorities to the four substituents on the chiral carbon atom. With the
lowest priority group pointing directly away from the viewer, we say that the
stereogenic center has an R-configuration if a curved arrow from the group of highest
priority through to the one of lowest priority is drawn in a clockwise direction.

(E)
(a)

Two compounds that are optical isomers of each otherthey have different locations
of the substituent groups around their chiral carbonsbut are not mirror images of
each other are diastereomers.

(b)

Two isomers that are nonsuperimposable mirror images of one other are called
enantiomers.

(c)

( ) is another way of designating a levorotatory compound.

(d)

D indicates that, in the Fisher projection of the compound, the OH group on the
penultimate carbon atom is to the right and the H group is to the left.

(E)
A reducing sugar has a sufficient amount of the straight-chain form present in equilibrium
with its cyclic form such that the sugar will reduce Cu 2+ aq to insoluble, red Cu 2 O s .
Only free aldehyde groups are able to reduce the copper(II) ion down to copper (I).

b g

bg

Next, we need to calculate the mass of Cu2O expected when 0.500 g of glucose is oxidized
in the reducing sugar test:
mass Cu 2 O (g) =

1 mol glucose
2 mol Cu 2+ 1 mol Cu 2 O 143.1 g Cu 2 O

0.397g Cu 2 O
180.2 g glucose 1 mol glucose 2 mol Cu 2+ 1 mol Cu 2 O

1312

Chapter 28: Chemistry of the Living State

20.

(D) The eight aldopentoses are drawn below as Fischer structures.


Note: There are 4 pairs of enantiomers and each structure has 6 diasteromers.
CHO

mirror

mirror
CHO

H C OH HO C H
H C OH HO C H
H C OH HO C H
CH2OH
CH2OH
enantiomers

CHO

CHO
HO C H
H C OH
H C OH HO C H
H C OH HO C H
CH2OH
CH2OH
enantiomers

mirror
CHO
CHO
HO C H
HO C H

CHO mirror CHO

H C OH
H C OH HO C H
H C OH HO C H
H C OH

HO C H
H C OH
H C OH HO C H
CH2OH
CH2OH
CH2OH
CH2OH
enantiomers
enantiomers

21.

(E) Enantiomers are alike in all respects, including in the degree to which they rotate
polarized light. They differ only in the direction in which this rotation occurs. Since glucose and -glucose rotate the plane of polarized light by different degrees, and in the
same direction, they are not enantiomers, but rather diastereomers.

22.

(M) We let x represent the fraction of -D-glucose. Then 1 x is the fraction of -Dglucose.

c h b gc

+52.7 = x 112 + 1 x 18.7 = 112 x +18.7 18.7 x = 93 x +18.7


x=

52.7 18.7
= 0.37
93

The solution is 37% -D-glucose; and thus 63% -D-glucose.

Fischer Projections and R, S Nomenclature


23.

(E)
(a)
(b)
(c)
(d)

24.

(E)
(a)
(b)
(c)
(d)

Enantiomers: S-configuration (leftmost structure), R-config. (rightmost structure)


Different molecules: different formulas
Diasteriomers: S,R configuration (leftmost structuretop to bottom),
S,S-configuration. (rightmost structure)
Diasteriomers: R,R-configuration (leftmost structuretop to bottom),
R, S-configuation (rightmost structuretop to bottom)
Same molecule: both R-configuration
Same molecule: both R-configuration
Enantiomers: S,S-configuation (leftmost structure), R,R-config. (rightmost structure)
Diasteriomers: S,R-configuration (leftmost structuretop to bottom),
R, R-configuration (rightmost structure)

1313

Chapter 28: Chemistry of the Living State

25.

(M)
CO2H

H
Cl

CH3

H3C

Cl

CH3

HO

CH3

HO

Br

OHC

OH

H3C

NH2

CH3

CH3

H
(a)

26.

CO2H2

H
(c)

(b)

Cl
(d)

(M)
Br

Br
H

CH3

CH3

Cl

Br

CH3

CH3
(a)

NH2
H

CH3 OHC

OH

H3C

HO

CO2H
(c)

(b)

OH

CO2H
(d)

HO2C

HO

CO2H
(e)

Amino Acids, Polypeptides, and Proteins


27.

(E)
(a)

(b)

An -amino acid has an amine group (NH2) bonded to the same carbon as the
carboxyl group (COOH). For example: glycine H 2 NCH 2 COOH is the simplest
-amino acid.
A zwitterion is a form of an amino acid in which the amine group is protonated
NH 3 + and the carboxyl group is deprotonated COO . For instance, the

zwitterion form of glycine is + H 3 NCH 2 COO .


(c)

The pH at which the zwitterion form of an amino acid predominates in solution is


known as the isoelectric point. The isoelectric point of glycine is pI = 6.03 .

(d)

The peptide bond is the bond that forms between the carbonyl group of one amino acid
and the amine group of another, with the elimination of a water molecule between
them. The peptide bond between two glycine molecules is shown as a bold dash
(
) in the structure below.
O
H2N

(e)

CH2

O
O

NH

CH2

C OH

Tertiary structure describes how a coiled protein chain further interacts with itself to
wrap into a cluster through a combination of salt linkages, hydrogen bonding, and
disulfide linkages, to name a few.

1314

Chapter 28: Chemistry of the Living State

28.

29.

(E)
(a)

A polypeptide is a long chain of amino acids, joined together by peptide bonds.

(b)

A protein is another name for a polypeptide, but a distinction is often made. Proteins
are longer chains than polypeptides, and proteins are biologically active.

(c)

The N-terminal amino acid in a polypeptide is the one at the end of the polypeptide
chain that possesses a free NH 2 . The N-terminal amino acid is at the left end of the
structure of diglycine in the answer to the previous exercise.

(d)

An helix is a natural secondary structure adopted by many proteins. It is rather like


a spiral rising upward to the right (that is, clockwise as viewed from the bottom). This
is a right-handed screw. The alpha helix is shown in Figure 27-12.

(e)

Denaturation is that process in which at least some of the structure of a protein is


disrupted, either thermally (with heat), mechanically, or by changing the pH or the
ionic strength of the medium in which the protein is enveloped. Denaturation is
accompanied by a decrease in the biological activity. Denaturation can be temporary or
permanent.

(M) The pI of phenylalanine is 5.74. Thus, phenylalanine is in the form of a cation in 1.0 M
HCl ( pH = 0.0 ), an anion in 1.0 M NaOH ( pH = 14.0 ), and a zwitterion at pH = 5.7 . These
three structures follow.
NH2
NH3 Cl

CH2
(a)

CH2

CH COOH
(b)

NH3
CH2

CH COONa

CH COO

(c)

30.

(M) The pI of histidine is 7.6. Thus, histidine is in the form of a cation at pH = 3.0), an anion
at pH = 12.0), and a zwitterion at pH = 7.6. These three structures follow.
(a) N

(b) N

pH = 3.0
N
H

(c) N

CH2CH(NH3+)CO2H

pH = 12.0
N
H

pH = 7.6

CH2CH(NH2)CO2-

1315

CH2CH(NH3+)CO 2-

Chapter 28: Chemistry of the Living State

31.

(E)
(a)

alanylcysteine
O

H2N CH

C NH

CH3

CH

C OH

CH2
SH

(b)

threonylvalylglycine
O

H2N CH

C NH CH

C OH

C NH CH

CHOH H3C CH

32.

CH3

CH3

(E)
(a)
H 2N

CH

(C H 2 )2
S

(b)

C H3

O
NH

CH

C NH

NH

CH

CH

H 3C

CH

CHOH

CH2

C H3

CH 3

SH

OH

methionylvalylthreonylcysteine

33.

(M) pH = 6.3 is near the isoelectric point of proline (6.21). Thus proline will not migrate
very effectively under these conditions. But pH = 6.3 is considerably more acidic than the
isoelectric point of lysine ( pI = 9.74 ). Thus, lysine is positively charged in this solution
and consequently will migrate toward the negatively charged cathode.
Furthermore, pH = 6.3 is much less acidic than the isoelectric point of aspartic acid
( pI = 2.96 ). Aspartic acid, therefore, is negatively charged in this solution and
consequently will migrate toward the positively charged anode.

34.

(M) pI = 5.74 is the isoelectric point of phenylalanine. Thus phenylalanine will not migrate.
But pH = 5.7 is more acidic than the isoelectric point of histidine ( pI = 7.58 ). Thus, histidine
is positively charged in this solution and will migrate toward the negatively charged cathode.
And pH = 5.7 is less acidic than the isoelectric point of glutamic acid ( pI = 3.22 ). Glutamic
acid is negatively charged in this solution; it will migrate to the positively charged anode.

1316

Chapter 28: Chemistry of the Living State

35.

(M)
(a) in strongly acidic solution
+
H 3 NCH(CHOHCH 3 )COOH

(b)

at the isoelectric point

H 3 NCH(CHOHCH 3 )COO

H3N

CH

H3N CH

OH

CHOH

CHOH

CH3

CH3

in strongly basic solution H 2 NCH(CHOHCH 3 )COO

(c)

O
H2N CH

CHOH
CH3
36.

(M)
(a) aspartic acid

(b)

(c)

H 3N

CH

OH

H3N CH

CH3

NH2
COOH
H2NCH(CH2COOH)COO H3NCH((CH 2)4NH2)COOH

(D)
(a)

(CH 2) 4

CH2

37.

alanine

O
H2N CH

lysine

H3NCH(CH3)COO

The structures of the six tripeptides that contain one alanine, one serine, and one lysine
are drawn below (in no particular order).
Lys-Ser-Ala (1 of 6)
O
NH 2

CH

(C H 2)4

O
NH

CH

CH 2OH

NH2

1317

O
NH

CH
CH 3

OH

Chapter 28: Chemistry of the Living State

Lys-Ala-Ser (2 of 6)
O
NH 2

CH

O
NH

( C H 2 )4

CH

O
NH

CH 3

CH

OH

CH 2OH

N H2

Ser-Lys-Ala (3 of 6)
O
NH 2

CH

O
NH

C H 2O H

CH

O
NH

(CH 2)4

CH

OH

CH 3

NH 2

Ser-Ala-Lys (4 of 6)
O
NH 2

CH

O
NH

C H 2OH

CH

O
NH

CH 3

CH

OH

(CH 2)4
NH2

Ala-Ser-Lys (5 of 6)
O
NH 2

CH

O
NH

CH3

CH

O
NH

CH 2OH

CH

OH

(CH 2)4
NH2

Ala-Lys-Ser (6 of 6)
O
NH 2

CH
CH3

O
NH

CH

O
NH

(CH 2)4

CH

CH 2OH

NH 2

1318

OH

Chapter 28: Chemistry of the Living State

(b)

The structures of the six tetrapeptides that contain two serine and two alanine amino
acids each follow (in no particular order).
Ala-Ser-Ala-Ser (1 of 6)
O

O
NH 2

CH

NH

CH 3

Ala-Ala-Ser-Ser (2 of 6)

CH

CH

NH

CH 2OH

O
NH 2

CH

CH3

CH

NH

CH

CH 3

CH

OH

O
NH

CH 2OH

CH 3

O
NH

NH

CH

CH 2OH

CH 2OH

OH

Ala-Ser-Ser-Ala (3 of 6)
O
NH 2

CH

O
NH

CH3

CH

NH

CH

CH 2OH

CH 2OH

NH

CH

OH

CH 3

Ser-Ser-Ala-Ala (4 of 6)
O
NH 2

CH

NH

C H 2O H

CH

NH

CH

O
NH

OH

CH 3

CH 3

CH 2OH

CH

Ser-Ala-Ser-Ala (5 of 6)
O
NH 2

CH

O
NH

C H 2OH

CH

O
NH

CH

NH

OH

CH 3

CH 2OH

CH 3

CH

Ser-Ala-Ala-Ser (6 of 6)
O
NH 2

CH

C H 2O H

O
NH

CH
CH 3

1319

O
NH

CH
CH 3

NH

CH

CH 2OH

OH

Chapter 28: Chemistry of the Living State

38.

(M) There are twenty four possible combinations. They are listed below.
Ala-Lys-Ser-Phe
Lys-Ala-Ser-Phe
Ser-Ala-Phe-Lys
Phe-Ala-Ser-Lys
Ala-Lys-Phe-Ser
Lys-Ala-Phe-Ser
Ser-Ala-Lys-Phe
Phe-Ala-Lys-Ser
Ala-Ser-Lys-Phe
Lys-Ser-Phe-Ala
Ser-Lys-Phe-Ala
Phe-Lys-Ser-Ala
Ala-Ser-Phe-Lys
Lys-Ser-Ala-Phe
Ser-Lys-Ala-Phe
Phe-Lys-Ala-Ser
Ala-Phe-Ser-Lys
Lys-Phe-Ser-Ala
Ser-Phe-Ala-Lys
Phe-Ser-Ala-Lys
Ala-Phe-Lys-Ser
Lys-Phe-Ala-Ser
Ser-Phe-Lys-Ala
Phe-Ser-Lys-Ala

39.

(M)
(a) We put the fragments together as follows, starting from the Ala end, and then placing
them in a matching pattern. We do not assume that the fragments are given with the Nterminal end first.

Fragments:

Result:
(b)
40.

Ala Ser
Ser

Ala Ser

Gly Val
Gly Val Thr
Val Thr
Val Thr
Gly Val Thr

alanyl-seryl-glycyl-valyl-threonyl-leucine, or alanylserylglycylvalylthreonylleucine

(M)
(a) We put the fragments together as follows, starting from the Ala end, and then simply
aligning them in a matching pattern. We do not assume that the fragments are given
with the N-terminal end first.

Fragments: Ala Lys Ser


Lys Ser
Ser
Result:
(b)

41.

3rd fragment
1st fragment
5th fragment
2nd fragment, reversed
Leu 4th fragment, reversed
Leu

Ala Lys Ser

1st fragment
Gly
5th fragment
Gly
3rd fragment
Gly Phe
4th fragment
Gly Phe Gly 2nd fragment
Gly Phe Gly

alanyl-lysyl-seryl-glycyl-phenylalanyl-glycine, or
alanyllysylserylglycylphenylalanylglycine

(E)
The primary structure of an amino acid is the sequence of amino acids in the chain of the
polypeptide. The secondary structure describes how the protein chain is folded, coiled, or
convoluted. Possible structures include -helices and -pleated sheets. These secondary
structures are held together principally by hydrogen bonds. The tertiary structure of a
protein refers to how different parts of the molecules, often quite distant from each other,
interact with each other to maintain the overall shape of the protein macromolecule.
Although hydrogen bonding is involved here as well, disulfide linkages, hydrophobic
interactions, and hydrophilic interactions (salt linkages) are responsible as well for tertiary

1320

Chapter 28: Chemistry of the Living State

structure. Finally, quaternary structure refers to how two or more protein molecules pack
together into a larger protein complex. Not all proteins have a quaternary structure since
many proteins have only one polypeptide chain.
42.

(E) The difference between sickle cell hemoglobin and normal hemoglobin is due solely to
the substitution of one amino acid for another (valine for glutamic acid) at one position in
the entire protein. This changes the quaternary structure of the hemoglobin. The sickle cell
defect arises from the mistaken incorporation of one molecule for another during protein
synthesis. This is why the name molecular disease is apt.

43.

(M)

CH3
H2N

R-alanine

CO2H
44.

(M)

CH2OH
H2N

R-serine

CO2H
45.

(D)

CH3
H

NH2

CO2H
S-alanine
46.

H
H2N

CH2C6H5

CH2C6H5

CH3
CO2H

NH2

CO2H

H
H2N

S-phenylalanine

S-alanine

S
CO2H

S-phenylalanine

(D)
HO2C

R
H
R-proline

NH

H
HO2C

CH2

R
N
H
R-proline

1321

CH(CH3)2

CH(CH3)2

H2C CH2
H

NH2

CO2H
S-valine

H
H2N

S
CO2H
S-valine

Chapter 28: Chemistry of the Living State

Nucleic Acids
47.

(E) Two major types of nucleic acids are DNA (deoxyribonucleic acid), and RNA
(ribonucleic acid). Both of them contain phosphate groups. These phosphate groups alternate
with sugars to form the backbone of the molecule. The sugars are deoxyribose in the case of
DNA and ribose in the case of RNA. Attached to each sugar is a purine or a pyrimidine base.
The purine bases are adenine and guanine. One pyrimidine base is cytosine. In the case of
RNA the other pyrimidine base is uracil, while for DNA the other pyrimidine base is
thymine.

48.

(E) The thread of life is an apt name for DNA, being both a literal and a figurative
description. It is literal in that it is thread-like, long and narrow, in shape and is an essential
molecule for life. It is figurative in that DNA is essential for the continuance of life and runs
like a thread through all stages in the life of the organism, from origin through growth and
reproduction to final death.

49.

(D) The complementary sequence to AGC is TCG. One polynucleotide chain is completely
shown, as is the hydrogen bonding to the bases in the other polynucleotide chain. Because of
the distortions that result from depicting a 3-D structure in two dimensions, the H- bonds
themselves are distorted (they are all of approximately equal length) and the second sugar
phosphate chain has been omitted.
CH3
O
H

N
O

O
O

P
OH

OCH2 N
O

O
O OH

P
OH

OCH2 N
O

N
N
H

P
OH

H
N

OCH2
N
O

N
O

H
H

O OH

OH

1322

H N
H

Chapter 28: Chemistry of the Living State

50.

(D) The complementary sequence to TCT is AGA. One polynucleotide chain is completely
shown, as is the hydrogen bonding to the bases in the other polynucleotide chain. Because of
the distortions that result from depicting a three-dimensional structure in two dimensions, the
hydrogen bonds themselves are distorted (they are all of approximately equal length) in the
diagram.
OH
N

A
O

O
H3C

N
H

O
O P O CH2
OH

N
N

H
H

H
OH

N
N

H3C

H
N

O
T

A
O

OH
H2C O P O

O P O CH2
OH

N
N

OH

OH
CH2 O P O

OH

G
O

N
H

O P O CH2
OH

H
N

O
C

N
O

OH

O
T

OH
CH2 O P O

OH

Integrative and Advanced Exercises


51. (E) M

100.00 g hemoglobin 55.85 g Fe


4 mol Fe

6.6 10 4 g/mol hemoglobin.


0.34 g Fe
1 mol Fe 1 mol hemoglobin

52. (E) If we assume that there is only one active site per enzyme and that a silver ion is necessary
to deactivate each active site, we obtain the molar mass of the protein as follows.
1.00 mg
1 mol
1 mol Ag
1g
molar mass

2.9 103 g/mol

0.346 mol Ag mol 1 mol protein 1000 mg


This is a minimum value because we have assumed that 1 Ag+ ion is all that is necessary to
denature each protein molecule. If more than one silver ion were required, the next to last
factor in the calculation above would be larger than 1 mol Ag+/1 mol protein, and the molar
mass would increase correspondingly.

1323

Chapter 28: Chemistry of the Living State

53. (M) Triolein tristearin


O
O O

Triolein (901.44 g/mol)


C57H104O7

O O
O
O

3 H2(g)

O O

Tristearin (907.49 g/mol)


C57H110O7

O O
O

3 mol H 2
1 mol triolein

= 51.6 mol H 2
0.90144 kg triolein 1 mol triolein
CO(g) + 3 H2(g)
92.0 %
CH4(g) + H2O(g)
C2H6(g) + 2 H2O(g) 2 CO(g) + 5 H2(g)
8.0 %
Consider 1.00 L Determine the moles of H2 formed.
1.00 L of natural gas contains 0.920 L CH4 and 0.080 L C2H6
n H2 = 15.5 kg triolein

1atm
756 mmHg
(0.920 L)
760 mmHg

n CH4 =
= 0.03734 mol CH 4
(0.08206 L atm K -1mol-1 )(25.5 + 275.15 K)

1atm
756 mmHg
(0.080 L)
760 mmHg

n C2 H6 =
= 0.00325 mol C2 H 6
(0.08206 L atm K -1mol-1 )(25.5 + 275.15 K)
n H2 (CH 4 ) = n CH4 3 = 0.112 mol H 2
n H2 (C2 H 6 ) = n C2 H6 5 = 0.016 mol H 2

n H2 (total) = n H2 (CH 4 ) + n H2 (C2 H 6 ) = 0.112 mol H 2 + 0.016 mol H 2 = 0.128 mol H 2


Hence,1.00 L of natural gas gives 0.128 moles of H 2
Vnatural gas = 51.6 mol H 2

1.00 L natural gas


= 403L natural gas
0.128 mol H 2

1324

Chapter 28: Chemistry of the Living State

54. (D) Structures of the 16 aldohexoses identification of enantiomers


CHO

CHO

CHO

CHO

CHO

CHO

OH HO

OH HO

OH HO

OH HO

OH HO

OH HO

OH HO

OH HO

L-Allose

Enantiomers
CHO

CHO

CHO

HO

OH

OH

CH2OH

CH2OH

CHO

CH2OH

L-Idose L-Glucose

Enantiomers

CHO

CHO

HO

OH
CH2OH

D-Idose

CH2OH

Enantiomers

OH

HO

OH

HO

OH
OH

HO

OH HO
CH2OH

OH
CH2OH

CH2OH

D-Manose L-Glucose
L-Gluose

Enantiomers

CHO

OH HO

OH HO

HO

OH
CH2OH

Enantiomers

OH HO

OH HO

CH2OH

HO

HO

OH HO

OH HO
HO

CH2OH

CHO

OH HO

OH

D-Altrose L-Galactose L-Altrose D-Galactose

Enantiomers

OH HO

D-Glucose

D-Talose

CHO

CHO
HO
OH HO

OH HO

CH2OH

CH2OH

CH2OH

D-Allose L-Talose

OH

OH

HO

OH HO
CH2OH

HO

CH2OH

D-Glucose
D-Gluose

L-Manose

Enantiomers

Enantiomers

55. (M) As alluded to by the problem, there are eight possible aldopentoses, or more precisely, the
L- and D- isomers of four aldopentoses: Ribose, Arabinose, Xylose, and Lyxose.
CHO

CHO

CHO

OH

HO

OH

OH

HO

OH

OH

CH2OH

D-Ribose

CH2OH

HO

OH

OH

HO

HO

HO

HO

HO

HO

CH2OH

D-Lyxose
CHO
H

OH

OH

OH

H
CH2OH

L-Arabinose

L-Xylose

The sets of epimers are:


D-Ribose
D-Arabinose
D-Arabinose
L-Xylose
D-Xylose
D-Lyxose
L-Lyxose

OH
CH2OH

CHO

HO

L-Ribose

HO

D-Xylose

CHO

CH2OH

OH

CH2OH

D-Arabinose

CHO

CHO

HO

H
CH2OH

L-Lyxose

D-Xylose

D-Lyxose

D-Lyxose
L-Arabinose

L-Ribose

Of course, using the L- isomers of the above aldopentoses yields the complementary result.
1325

Chapter 28: Chemistry of the Living State

56. (M) The pI value is the pH at the second equivalence point, much like the pH of HPO42 is
pI 12 (pK a 2 pK a 3 ).

pK I 12 (pK a 2 pK a 3 ) 12 (8.65 10.76) 9.71

highly acidic form H 3 NCH 2 CH 2 CH(NH 3 )COOH

acidic form

H 3 NCH 2 CH 2 CH(NH 3 )COO

H 2 NCH 2 CH 2 CH(NH 3 )COO

zwitterion
pK a 1 1.94

pK a 2 8.65

pK a 3 10.76

57. (D) We represent the division and replication of DNA in the following diagram.
15
parents :
N || 15 N
15
14
N || 14 N
N || 15 N
1st
Subsequent division then occurs as follows. Note that each double strand in the first
generation contains one strand (of the two) that is nitrogen-15 labeled.
15
N||14N
1st (fraction 15N: 0.5):
nd
15
15
14
14
N||14N
2 (fraction N: 0.25): N|| N
14

3rd (fraction 15N: 0.125): 15N||14N


4th (fraction 15N: 0.0625):
15

N || 14 N

14

N || 14 N

14

N || 14 N

14

N || 14 N

14

N||14N

N || 14 N

14

14

14

N||14N

N || 14 N 14 N || 14 N

14

N||14N

N || 14 N

We see that, out of the eight double strands of DNA produced in the third generation, only one
of them incorporates 15N. Thus, one eighth of the DNA incorporates 15N.
58. (D) Assume all the fragments are given with the N-terminal end listed first. Since there is Arg
at the N-terminal end (and only two Arg amino acids), we begin with the fragment that starts
with an Arg residue and build the chain from there, making sure to end with an Arg fragment.
Fragments:
Arg
Pro
Pro
Pro
Pro
Gly
Pro
Gly
Phe
Gly
Phe
Ser
Pro
Ser
Pro
Phe
Pro
Phe Arg
Phe Arg
Nonapeptide: Arg
Pro
Pro
Gly
Phe
Ser
Pro
Phe Arg

1326

Chapter 28: Chemistry of the Living State

59. (D)
Amino Acid
serine

Messenger RNA
DNA
AGA
UCU
AGG
UCC
AGT
UCA
AGC
UCG
CCA
glycine
GGU
CCG
GGC
CCT
GGA
CCC
GGG
CAA
valine
GUU
CAG
GUC
CAT
GUA
CAC
GUG
CGA
alanine
GCU
CGG
GCC
CGT
GCA
CGC
GCG
One example for the required sequence would be AGA CCA CAA CGA. The redundancy
enables the organism to produce a given amino acid in several ways in case of transcription
error. For example, CG and any third DNA nucleotide will yield alanine in the polypeptide
chain.
60. (D) Sketch of the titration curve for threonine in 1 M HCl

10

pKa2 = 9.12

8
pH 6

pI =

pKa1 + pKa2
= 5.64
2

4
pKa1 = 2.15

[H3O ] = 1.00 M (1.00 M HCl)

0
Volume (mL)
COOH
H3N

H
R

50/50
mixture

of Base

COOH
H2N

H
R

50/50
mixture

COO
H2N

H
R

1327

predominant
species in
solution

Chapter 28: Chemistry of the Living State

61. (D)
(a) Consider successive 90 rotations in a Fischer projection of the chiral molecule R(+)
Glyceraldehyde
CHO
H R OH

o
90
clockwise

HOH2C

CH2OH
o
90
clockwise

270o
clockwise

CHO

OH
clo 180 o
ck
wi
se

OH
OHC

90

CH2OH

o
90
clockwise

Each 90 rotation about the


chiral carbon atom results
in an inversion of the
stereochemistry at the
chiral carbon atom.

CH2OH

HO R H

clockwise

CHO

(b) Consider interchange of two groups on chiral carbon atom in the molecule R(+) Glyceraldehyde
CHO

interchange
H R OH H and CHO OHC
CH2OH
interchange

H
S

OH

CH2OH

interchange
OH and CH2OH

OHC

R CH2OH
OH

H and CHO

Each interchange of two groups on the chiral carbon atom results in an inversion of the
stereochemistry at the chiral carbon atom. The effect of two such interchanges results in
the regeneration of the same molecule (enantiomer). The trivial case of interchanging the
same two groups twice shows that two interchanges result in the same molecule being
represented.
62. (M) Reaction of the pentapeptide with DFNB indicates that Met is the N-terminal end. The
remaining information provides the following possible sequences of fragments.

(1) Met

Met Gly or

(2) Met

Met

(3) Ser

Met

(4) Met

Met Ser

or

Met

Gly Met

Met Ser

Met

The fact that no fragment contains both Ser and Gly is strong evidence that these two amino
acids are not adjacent in the chain. In fact, there must be a Met between them. Experiment (2)
indicates that two Met residues are adjacent. Experiments (1) and (4), in combination with the
fact that Met is the N-terminal end, mean that a Gly-Met-Ser or a Ser-Met-Gly sequence
cannot end the chain. Hence,
Met
Gly Met Met Ser
or
Met Ser Met Met Gly
Experiment (3) confirms that the right-hand order above must be correct, for there is no way
that a dipeptide with Ser as the N-terminal end can be obtained from the left-hand order
above.

1328

Chapter 28: Chemistry of the Living State

63. (M)

COOH

COOH

H2N

H2N

H
R

R
R = H or CH

R = CH2SH

Most amino acids have the COOH as priority 2 and


the R group as priority 3. In cysteine, the R
group has priority 2 and the COOH group has
priority 3. Effectively, this is an interchange of the
two groups on a chiral carbon, resulting in an
inversion in the stereochemistry of the chiral carbon.

64. (M) Threonine (2S, 3R)-2-amino-3-hydroxybutanoic acid has four stereoisomersall are
shown below.

COOH

COOH
H2N

H R OH
CH3
2S, 3R

COOH

H R NH2
HO

CH3
2R, 3S

H2N

H R NH2

HO

H R OH

CH3
2S, 3S

Enantiomers

G o'
(30000 J)

12.1
RT
(8.31 J/K mol)(298.15 K)

(c) A ADP Pi
B ATP

CH3
2R, 3R

Enantiomers

65. (D)
(a) G o' RTlnK
G o'
23000 J
lnK

9.3
RT
(8.31J/K mol)(298.15 K)
(b) ln K

COOH

K e 9.3 9.3 105


K e12.1 1.8 105

so...

[B] [ADP][K][Pi]
1
coupled
2.25
(1.8 105 )(0.005) 2.25

[A]
[ATP]
400
uncoupled 9.3 105

2.4 104

1329

Chapter 28: Chemistry of the Living State

FEATURE PROBLEMS
66.

(D)
Glyceryl Tristearate
O
CH2
CH
CH2

O
O
O

Glyceryl Trioleate
O

C
O

(CH2)16CH3

CH2

C
O

(CH2)16CH3

CH

(CH2)16CH3

CH2

O
O

C
O

(CH2)7CH=CH(CH2)7CH3

C
O

(CH2)7CH=CH(CH2)7CH3

(CH2)7CH=CH(CH2)7CH3

Molar Mass = 885.45 g mol-1

Molar Mass = 891.5 g mol-1

(a)

Saponification value of glyceryl tristearate: mass of KOH


1 mol glyceryl tristearate
3 mol KOH
= 1.00 g glyceryl tristearate

891.5 g glyceryl tristearate 1 mol glyceryl tristearate


56.1056 g KOH

= 0.189 g KOH or 189 mg KOH Saponification value = 189


1 mol KOH
Iodine number for glyceryl trioleate: mass of I2
1 mol glyceryl trioleate
3 mol I2
= 100 g glyceryl trioleate

885.45 g glyceryl trioleate 1 mol glyceryl trioleate


253.81 g I 2

= 86.0 g I2 Iodine number = 86.0


1 mol I 2

(b)

As we do not know the types of substances present in castor oil and their percentages,
we will assume that castor oil is the only glyceryl tririciniolate.
O
CH2 O C (CH2)7CH=CHCH2CHOH(CH2)5CH3
O
CH

O C (CH2)7CH=CHCH2CHOH(CH2)5CH3
O

CH2 O

Glyceryl Tririciniolate
Molar Mass = 933.4 g mol-1

C (CH2)7CH=CHCH2CHOH(CH2)5CH3

Iodine number for glyceryl tririciniolate: mass of I2


= 100 g glyceryl tririciniolate
1 mol glyceryl tririciniolate
3 mol I 2
253.81g I 2

933.4 g glyceryl tririciniolate 1 mol glyceryl tririciniolate 1 mol I 2


= 81.6 g I2

Iodine number = 81.6


1330

Chapter 28: Chemistry of the Living State

Saponification value of glyceryl tririciniolate: mass of KOH = 1.00 g glyceryl tririciniolate


1 mol glyceryl tririciniolate
3 mol KOH
56.1056 g KOH

933.4 g glyceryl tririciniolate 1 mol glyceryl tririciniolate


1 mol KOH
= 0.180 g KOH or 180. mg KOH
Saponification value = 180.
If castor oil and the other components have similar saponification values, then we
would expect an overall saponification value of 180. However, if the remaining
substances have a saponification value of zero, the overall saponification value is
expected to be ~160 (90/100 180).
(c)

Safflower oil: Consider each component


Palmitic acid: Molar mass: C3H5(C15H31CO2)3 = 807.34 g mol1

Iodine number = 0 (saturated)


Saponification value of palmitic acid: mass of KOH
= 1.00 g palmitic acid
1 mol palmitic acid
3 mol KOH
56.1056 g KOH

807.33 g palmitic acid 1 mol palmitic acid


1 mol KOH
= 0.208 g KOH or 208 mg KOH

Saponification value = 208

Stearic acid: Molar mass: C3H5(C17H35CO2)3 = 891.49 g mol1

Iodine number = 0 (saturated)


Saponification value of stearic acid: mass of KOH
= 1.00 g stearic acid

1 mol stearic acid


3 mol KOH
56.1056 g KOH

891.49 g stearic acid 1 mol stearic acid


1 mol KOH

= 0.189 g KOH or 189 mg KOH

Saponification value = 189

Oleic acid: Molar mass: C3H5(C17H33CO2)3 = 885.45 g mol1

Iodine number for oleic acid: mass of I2


= 100 g oleic acid

253.81 g I 2
1 mol oleic acid
3 mol I 2

= 86.0 g I2
885.45 g oleic acid 1 mol oleic acid
1 mol I 2

Iodine number = 86.0


Saponification value of oleic acid: mass of KOH
= 1.00 g oleic acid

1 mol oleic acid


3 mol KOH
56.1056 g KOH

885.45 g oleic acid 1 mol oleic acid


1 mol KOH

= 0.190 g KOH or 190. mg KOH

1331

Saponification value = 190.

Chapter 28: Chemistry of the Living State

Linoleic acid: Molar mass: C3H5(C17H31CO2)3 = 879.402 g mol1

Iodine number for linoleic acid: mass of I2


= 100 g linoleic acid
= 173 g I2

253.81 g I 2
1 mol linoleic acid
6 mol I 2

879.402 g linoleic acid 1 mol linoleic acid


1 mol I 2

Iodine number = 173

Saponification value of linoleic acid: mass of KOH


= 1.00 g linoleic acid

1 mol linoleic acid


3 mol KOH
56.1056 g KOH

879.402 g linoleic acid 1 mol linoleic acid


1 mol KOH

= 0.191 g KOH or 191 mg KOH

Saponification value = 191

Linolenic acid: Molar mass: C3H5(C17H29CO2)3 = 873.348 g mol1


Iodine number for linolenic acid: mass of I2

= 100 g linolenic acid

1 mol linolenic acid


9 mol I 2
253.81 g I 2

873.354 g linolenic acid 1 mol linolenic acid


1 mol I 2

= 261.6 g I2

Iodine number = 261.6 262

Saponification value of linolenic acid: mass of KOH


= 1.00 g linolenic acid

1 mol linolenic acid

3 mol KOH

873.354 g linolenic acid 1 mol linolenic acid

= 0.193 g KOH or 193 mg KOH


Summary:
Acid
Palmitic
Stearic
Oleic
Linoleic
Linolenic

56.1056 g KOH
1 mol KOH

Saponification value = 193

High I2 # Low I2 # High Sap# Low Sap#


%
%
%
%
I2# Sap# %
0
208 6-7
6
7
7
6
0
189 2-3
2
3
2
3
86 190 12-14
12
14
12
14
173 191 75-80
78.5
75.5
87.5
76.5
262 193 0.5-1.5
1.5
0.5
1.5
0.5

Hence: The iodine number for safflower oil may range between 150 to 144.
The saponification value for safflower oil may range between 211 and 179.
(Note:the high iodine number contribution for each acid in the mixture is calculated
by multiplying its percentage by its iodine number. The sum of all of the high iodine
number contributions for all of the components in the mixture equals the high iodine
number for safflower oil. Similar calculations were used to obtain the low iodine
number, along with the high/low saponification numbers.

1332

Chapter 28: Chemistry of the Living State

67.

(D)
(a)
O

CHO
H

OH

H
Br2, H2O
Ca(OH)2

2+
O (Ca )1/2

+ CO2(g)

OH

CHO
HO

CHO
H2O2
Fe3+

H2O2
Fe3+

OH

OH

OH

Br2, H2O
HO
Ca(OH)2
H

OH

OH

OH

HO

HO

CH2OH

HO

CH2OH

CH2OH

D-Glucose

H
H
OH
OH
CH2OH

D-Arabinose

D-Manose

(b)
O
CHO
H

OH

OH
CH2OH

Br2, H2O
Ca(OH)2

2+
O (Ca )1/2

CHO

+ CO2(g)

OH

OH
CH2OH

D-Erythrose

H2O 2
Fe3+

CHO
H

OH

HO
H2O 2
Fe3+

CH2OH
D-Glyceraldehyde

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Br2, H2O H
Ca(OH)2

H
OH
CH2OH
D-Threose

Chapter 28: Chemistry of the Living State

H3
R or S
config.

O+

O
H

CHO

OH HCN(aq)
basic
CH2OH condition

OH

CH2OH
H3O+

D-Glyceraldehyde

H S C

N
H3O+
H R OH
heat
CH2OH
or
OH
N C

HO2C
O+

H R OH H3
heat
CH2OH

R or S
config.
CHO
HO

CH2OH

HCN(aq)
basic
condition

L-Glyceraldehyde

(d)

O
H
HO

C
S

CH2OH
H3O+

H S C

N
H3O+
HO S H
heat
CH2OH
or
OH
N C
HO

R
S

R
R

heat

HO2C
HNO3
OH
H

CH2OH

H Meso
form
S OH
R

CO2H

trihydroxy
butanoic acid

tartaric
acid

OH

OH

H S CO2H
HNO3
HO S H
CH2OH
or
OH

HO2C
H3O+

OH

H S CO2H
H S CO2H
HNO3
H R OH
H S OH Optically
active
CH2OH
CO2H
or
or
OH
OH

OH
H3O+

Diastereomers

OH

OH

(M)

Diastereomers

Diastereomers

68. (a-c)

HO

R
S

HO

CO2H
H

Meso
form

CO2H
or
OH

R
HO2C
H
Optically
HNO3
H
HO OR H active

CH2OH

CH2OH

Diastereomers

Diastereomers

CO2H
Diastereomers

Meso form of Tartaric acid Meso form is not optically active because one end of
the molecule rotates polarized light by +x degrees,
HO
O
C
while the other end of the molecule rotates it by x
degrees. The net result is that polarized light is
H
OH mirror
unaffected by this type of compound, even though it
H
OH plane
has two chiral carbons. Meso forms must have a mirror
image running through them; for every chiral carbon,
C
HO
O
there must exist its mirror image on the other side of
the molecule.

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Chapter 28: Chemistry of the Living State

SELF-ASSESSMENT EXERCISES
69.

(E)
(a) (+): Notation to indicate that a compound rotates the plane of polarized light in a
dextrorotatory (right-handed) direction.
(b) (L): The Fischer notation to indicate that the molecule has a levorotatory configuration.
(c) Sugar: A mono- or oligosaccharide. Saccharides are cyclic hydroxyketone or
hydroxyaldehyde
(d) -amino acid: An amino acid is a compound that has both a carboxylic acid (-COOH)
and an amino (-NH2) group. An -amino acid is one that has the amino group on the carbon, which is the carbon adjacent to the carboxylic group.
(e) Isoelectric point: The pH at which an ionic molecule has no net electric charge.

70.

(E)
(a) Saponification: The process of turning a triglyceride into a soap by hydrolyzing it to
glycerol and fatty acid salt.
(b) Chiral carbon atom: A carbon atom in a molecule which is sp3 hybridized and is bonded
to four different constituents.
(c) Racemic mixture: A mixture of R and S isomers of a compound in equal amounts. This
mixture does not rotate a plane of polarized light.
(d) Denaturation of protein: A mechanical/chemical process by which a protein loses its
tertiary (overall shape and folding) and possibly its secondary (local structure like -helix
or -sheet) structure.

71.

(E)
(a) Fat vs. oil: Both are triglycerides. However, fats are glyceryl esters in which saturated
fatty acid components predominate, making them solid at room temperature. In oils,
unsaturated fatty acids predominate, making them liquids at room temperature.
(b) Enantiomer vs. diasteriomer: An enantiomer is a compound with chirality. Diastereomer
are stereoisomers that are not enantiomers (these compounds have two or more
stereocenters).
(c) Primary vs. secondary structure of protein: The primary structure of a protein involves
the amino acid sequence that comprises the protein. The secondary structure refers to the
shape of segments of protein and is determined by the amino acids comprising a segment
and the polarity of the solvent.
(d) DNA vs. RNA: Simply from a chemical standpoint, DNA is deoxyribonucleic acid; it is
made of pentose sugar 2-deoxyribose, and bases adenine, guanine, thymine, and cytosine.
RNA is ribonucleic acid; it is made of ribose, and the base uracil instead of thymine.
(e) ADP vs. ATP: ATP is adenosine triphosphate. It is made up of the nucleoside
adenosine, and three phosphate groups in series. It undergoes oxidative phosphorylation
to release energy, lose a phosphate, and convert to ADP, which is adenosine diphosphate.
Adenosine diphosphate converts to ATP using the energy provided by oxidation of food.

72.

(E) The answer is (b), oil. Glyceryl trilinoleate is a triglyceride containing three linolic acid
substituents. Linolic acid is unsaturated, making it likely that it is a liquid at room
temperature and therefore an oil.

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Chapter 28: Chemistry of the Living State

73.

(E) The answer is (d), neither to the left nor the right. DL-erythrose has two stereo-centers:
one which rotates a plane of polarized light in a dextrorotatory, and the other in a
levorotatotory fashion. The two centers cancel each other out in their effect in rotating a
plane of polarized light.

74.

(E) The answer is (a), -galactose. The only other possible alternative is D-(+)-glucose, but
it is a much more descriptive term identifying a specific stereoisomer of glucose.

75.

(E) The answer is (d), denaturation of protein. Heating the egg white causes the protein
tertiary and secondary structure to change and makes the protein molecules coagulate.

76.

(E) The answer is (e), ATP.

77.

(E) The answer is (c). Glycerol is part of the triglycerides.

78.

(E) The answer is (b), double helix.

79.

(M) Below is the structure of glyceryltripalmitate:


O

H2C

H2C

H2C

Based on the molecular structure, its MW = 224 (MW of palmitate) 3 + 42.06 (MW of
C3H6, glyceride) = 714.06 g/mol.
125 g Gly-tripalmitate(GTP)

80.

mol GTP
3 mol palmitate 1 mol Na(palm.)

714.06 g GTP
1 mol GTP
1 mol palm.

247 g Na(palm)
129 g sodium palmitate soap
1 mol Na(palm.)

(M) There are two major things to look for to determine if the chain is DNA or RNA: the
ribose/deoxyribose sugar and presence of uracil or thymine. Looking at the structure, it is
seen that the bases attached to the sugars down the right side of the structure are adenine
(purine), uracil (pyrimidine), guanine (purine), and cytosine (pyrimidine). Furthermore, the
sugar is ribose, making this an RNA chain.

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Chapter 28: Chemistry of the Living State

81.

(M) The answer is (e), none of these. Consulting Table 28.3, it is seen that the residue does
not match that of any amino acid given.

82.

(M) The answer is (b), 1,4-dichlorobutane. See structure below:


H

H
H

Cl

Cl
H

H H

83.

(E) The answer is (a), glycine. It is the only non-chiral amino acid, because the R group is
just H.

84.

(E) The answer is (d), they always rotate plane-polarized light.

85.

(E) The answer is (c), -CH(CH3)2.

86.

(E) The answer is (d), condensation. The carboxylic terminus from one amino acid reacts
with the amino terminus from another one to form a peptide bond and eliminate water.

87.

(E) The answer is (b.), Oleic acid.

88.

(D) Following the method in Example 28-2, the sequence is Gly-Cys-Val-Phe-Tyr.

89.

(M) In this chapter, the only overarching concept is biomolecules, which are molecules
needed for sustaining life. They either provide structure to the body, are metabolized by the
body, or are involved in information transfer. The main concepts falling under the
overarching concept of biomolecules are proteins, lipids, carbohydrates, and nucleic acids.
Proteins could further be described in terms of their primary, secondary, and tertiary
structures. The primary structure can be described in terms of the individual amino acids.
Secondary structure involves beta sheets or alpha helices. In this case of lipids, we can
further describe them in terms of triglycerides, both saturated and unsaturated. For nucleic
acids, we can further break them down in the terms of the major bases, ribose sugar, and
phosphate. Carbohydrates encompass many simpler concepts. Take a look at the subsection
headings and problems for more refining of the general and specific concepts.

1337