전단원 요약정리

Soonchunhyang University

Department of Chemical Engineering

Prof. Jungkyun Im

순천향대

나노화학공학과

임 정 균 교수

생유기화학

(Bioorganic Chemistry)

Free-Radical Chain-Growth Polymerization

In CH2 CH

X

In CH2 CH

X

Initiation:

Propagation: In CH2 CH

X

CH2 CHX

In CH2CH CH2 CH

X X

CH2 CHX

etc.

Termination: HC

X

+ CH

X(radical coupling)

HC

X

CH

X

CH2 HC

X

+ CH

X

CH2

disproportionation

CH2 + CH

X

C

X

CH

Chain Transfer (Hydrogen Abstraction)

HC

X

+ C

X

H

CH2

X

+ C

X

Synthetic Polymer

Cationic Chain-Growth Polymerization

and so onR+ + CH2 CH

X

CH2R CH

X

+

CH2 CH

X

Anionic Chain-Growth Polymerization

and so onR– + CH2 CH

X

CH2R CH

X

–

CH2 CH

X

Step-Growth Polymerization (illustrated for polyesters)

HO C

O

C

O

OH

OH2–

HO O C

O

C

O

OH

from diol from diacid

(two units)

+

HO OH

HO O C

O

C

O

OH

HO C

O

C

O

OH

or

HO OH

four units three units

Synthetic Polymer

Saponification of a Triglyceride

CH2 O C R

O

CH O C R

O

CH2 O C R

O

+ 3NaOH

CH2 O

CH O

CH2 O

+ 3 Na+ O C R

O

–

H

H

H

Hydrogenation of a Triglyceride (Hardening)

CH2 O C

O

CH O C

O

CH2 O C

O

CH2( )nCH CH CH2( )mCH3

CH2( )nCH CH CH2( )mCH3

CH2( )nCH CH CH2( )mCH3

H23

Ni, heat

CH2 O C

O

CH O C

O

CH2 O C

O

CH2( )n CH2( )mCH3CH2CH2

CH2( )n CH2( )mCH3CH2CH2

CH2( )n CH2( )mCH3CH2CH2

Lipid and detergent

Hydrogenolysis of a Triglyceride

H26

zinc chromite

CH2 O C

O

CH O C

O

CH2 O C

O

R

R

R

CH2 O

CH O

CH2 O

+ HOH RC2

H

H

H

1. Know the meaning of: triglyceride, fatty acid, fat, oil, hardening of a vegetable oil, hydrogenolysis, soap, saponification. 2. Know the structures and common names of the acids listed in Table 15.1. 3. Given the name of a glyceride, write its structure. 4. Given the name or structure of a carboxylic acid, write the formula for the corresponding glyceride.

요점 사항

Lipid and detergent

CH2HO

CH OH

CH

CH CH

CH OHO

OH OH

acyclic (aldehyde)

CH2HO

CH O

CH

CH CH

CHHO

OH OH

cyclic (hemiacetal)

OH

anomeric carbon

CH O

CHOH)

CH2OH

( n

aldose

H2OBr2 ,

or

Ag+ or Cu2+

CO

CHOH)

CH2OH

( n

aldonic acid

2H

CH O

CHOH)

CH2OH

( n

aldose

HNO3CO

CHOH)( n

aldaric acid

2H

CO2H

Acyclic ad Cyclic Equilibration

Oxidaton

polysaccharide H3O+

oligosaccharide H3O+

monosaccharide

Hydrolysis

Carbohydrate

Reduction

CH O

CHOH)

CH2OH

( n

aldose

H2, catalyst

orCHOH)

CH2OH

( n

alditol

NaBH4

CH2OH

Esterification and Etherification

Ac2O

OH

H OH

HH

OH

H

HO

OH2CH

O

Ac = CH3C

O

OAc

H OAc

HH

H

AcO

OH2CAc

O OAc

OH

H OH

HH

OH

H

HO

OH2CH

ONaOH, H3C( )2SO4

or

CH3 I, Ag2O

O

H O

HH

O

H

OH2C

OCH3O

CH3

CH3

CH3

CH3

Formation of Glycosides

OH

H OH

HH

OH

H

HO

OH2CH

O

H+

ROH

OH

H OH

HH

OR

H

HO

OH2CH

O

+ H2O

Carbohydrate

H

C CO2H

NH3+

R

HO–

H+

H

C CO2

NH3+

R–

HO–

H+

H

C CO2

NH2

R–

dipolar ion

H

C CO2

NH3

R–

+

+ R'OH + H+

H

C CO2 R'

NH3+

R + OH2

OH2

H

C CO2

NH3

R–

+

+ C ClR'

O

HO–2

CR'

O

NH

H

C CO2R–

+ 2 + Cl –

Dissociation of Amino Acids

Esterification

Acylation

Ninhydrin Reaction

N

O

O

OH

OH

+

H

C CO2

NH3

R–

+

2

O

O

O

O

+ RCHO + CO2 H2+ 3 O + H+

–

Amino acid, peptide, protein

H

C CO2

NH2

R H

base

H

C CO2

NH

R H

NO2

NO2

+ F–

F

NO2

NO2

+

N C S + NH2

H

C

R

C

O

N

H

N

H

C

S

N

H

C

R

H

C

O

N

HOH2

HCl

S

O

NNH

C H

R

+ NH2

= peptide chain

Sanger’s Reagent

Edman Degradation

Amino acid, peptide, protein

(CH3)3CO OC

O

C

O

OC(CH3)3 + NH3

R

C

H

1

CO2–

base

di- t -butyl dicarbonate

(CH3)3CO C

O

NH

R

C

H

1

CO2–

BOC or P

P NH

R

C

H

1

CO2

–+ Cl CH2

뺺l –

P NH

R

C

H

1

C

O

O CH2

= polymer

(CH3)3CO C

O

NH

R

C

H

1

C

O

O CH2

HCl

CH3CO2H

NH2

R

C

H

1

C

O

O CH2 + CO2 + (CH3)2C CH2

Peptide Synthesis

a. N-protection:

b. Polymer attachment:

c. Deprotection (removal of the protecting group):

Amino acid, peptide, protein

OH

H

H

O

O

P

O

OO–

N

H

Base

H2O

enzyme

OH

O

N

H

Base

OH

H

O

O

N

H

Base

H2O

H

HO–

O

P OO–

–

nucleotide

DNA segment

OH

H

O

N

H

BaseHO

nucleoside

H

OH

H

O

H

HO

2-deoxy-D-ribose

HO

+ HN-Base

H2O H+

heterocyclic

base

Hydrolysis of Nucleic Acids

Nucleic acid

1. Know the meaning of: nucleic acid, nucleotide, nucleoside.

2. Know the structures of: cytosine, thymine, adenine, guanine, uracil, 2-deoxy-D-ribose, D-ribose.

3. Know the meaning of: DNA, RNA, N-glycoside, pyrimidine base, purine base.

4. Given the name, draw the structure of a specific nucleoside.

5. Write an equation for the hydrolysis of a specific nucleoside by aqueous acid. Write the steps in the

reaction mechanism.

6. Given the name, draw the structure of a specific nucleotide.

7. Write an equation for the hydrolysis of a specific nucleotide by aqueous base.

8. Draw the structure of an N-glycoside and an O-glycoside.

9. Given the name or abbreviation for a DNA or RNA nucleotide or nucleoside, draw its structure.

10. Draw the primary structure of a segment of an RNA or DNA chain.

11. Explain why only pyrimidine-purine base pairing is permissible in the double helix structure.

12. Describe the main features of the secondary structure of DNA.

13. Explain, with the aid of structures, the role of hydrogen bonding in nucleic acid structures.

14. Describe the main features of DNA replication.

15. Given the base sequence in one strand of a DNA molecule, write the base sequence in the other

strand, or in the derived mRNA. Conversely, given a base sequence for mRNA, write the base sequence in one

strand of the corresponding DNA.

16. Given a synthetic polyribonucleotide and the peptide sequence in the resulting polypeptide, deduce

the codons for the amino acids.

17. Describe the main features of protein biosynthesis.

18. Explain the different functions of messenger, ribosomal, and transfer RNA.

19. Know the meaning of: codon, anticodon, genetic code, transcription, polymerase chain reaction.

요점 사항