첨단화학의 이해 synthesis make me a molecule biology materials chemistry

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첨첨첨첨첨 첨첨 Synthesis Make me a molecule Biology Materials Chemistry

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Page 1: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해Synthesis

Make me a molecule

Biology Materials

Chemistry

Page 2: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해DNA, Genes, and Proteins

Page 3: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해Genomics, Proteomics and Chemical Genetics

Genomics

Proteomics Chemical Genetics

Gene Sequence:- ~30,000 genes- unable to identify therapeutic targets- no protein function and disease relevance

Protein Function: - purification and structure determination- ~100,000 proteins in human - 75% no known cellular functions

Small Molecules: - modulate biological functions of proteins

ControlBiologicalFunctions

Drug Drug DiscoveDiscove

ryry

Page 4: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해

proteinnormalsignal activateactivate

protein functionprotein function

deactivatedeactivateprotein functionprotein function

falsesignal

Protein Function (Drug Action)

Page 5: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해

N

HNN

N

N

N

O

O

Viagra

(treatment of impotence)

N

N

CO2Et

Cl

Claritin(antihistamine,i.e. antiallergic)

NH

N

O

OH

S NHO

HO

H

H

Viracept

(treatment of AIDS)

NH

O

OO

F

Paxil

(psychotherapeutic)

F3C O NH

Prozac(antidepressant)

NHS

O

HO2C

Captopril

(treatment of hypertension)

N

N N

N

O

H2N

OHO

Acyclovir(antiviral)

N

N

Cl

O

Valium(tranquilizer)

HN OPt

O O

H2N NH2

Carboplatin

(treatment of ovarian cancer)

O

O

NMe2

NH2

Novocain

(local anesthetic)

Selected Medications of 20th Century

NH2

ClCl

Zoloft

(psychotherapeutic)

N

HN

S N

MeO

O

OMe

Prilosec

(antispasmodic)

OS

HN

N

NO2

HN

Zantac(treatment of ulcer)

N

HN

SNH

NH

NCN

Tagamet(treatment of ulcer)

Page 6: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해

HO

H

OH

H H

O

H

OH

H H

H

17-ethynylstradiol norethindrone

(the "Pill"; contraceptive)

O

O

OHHO OMe

O

O

O

HON

OMe

OH

Clarithromycin(antibacterial)

N

S

HOO

O

H H

CO2H

NH2

Ampicillin(antibiotic)

NO

H

CO2H

OH

Clavulanic acid(-lactamase inhibitor)

Augmentin(antibiotic)

Selected Medications of 20th Century

O

HO

RO

N

R= H MorphineR= Me Cocaine

(pain killer)

OO

O

OH

OH

R H

R= HR=Me

MevacorZocor

(treatment of high cholesterol)

Page 7: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해Target-Oriented Organic Synthesis

Known active sitesof target proteins

Design and synthesisof target molecules

biological effects

Page 8: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해

정상

이상

Diversity-Oriented Organic Synthesis

Library of diverse small molecules

unknown proteins

Page 9: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해

Combinatorial ChemistryCombinatorial Chemistry

Page 10: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해

44 = 256 개 tetramer

Combinatorial Library

4 개의 monomer

••••

Nn Combinations

Page 11: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해

resin +monomer

shakeresin

cleavage

wash

Solid Phase Synthesis 의 기본원리

wash

Page 12: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해Solid-Phase Synthesis of Peptides

polymerbead

amino acid

cleave

In 1960s, Bruce Merrifield: peptide synthesis from amino acids

peptide

Page 13: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해Solid Phase Library Synthesis

• polymer supported synthesis: easy purification

• fast generation of diverse library of molecules in few steps

• limited reactions compared to solution reactions

Split-Mix (split-pool) synthesis

Parallel synthesis

Page 14: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해Split-Mix Process

Mix-SplitCouple

Mix-SplitCouple

33= 27tag each bead!

Page 15: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해Parallel synthesis

- synthesis of small number of focused library

- no tagging beads!

Page 16: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해Solid Phase Library

203 = 8000 tripeptides

20 amino acids

202 = 400 dipeptides

204 = 160,000 tetrapeptides

In 1991s, Houghten & Lam: synthesis of a huge peptide library

peptide

DNA: fully automatic (solution)

Solid-phase synthesis

ln 1992, Jon Ellman: synthesis of non-peptide drug-like molecules by solid phase synthesis

carbohydrate

small molecule (drug-like)

Page 17: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해

2,180,106 compounds

Combination of Chemical Building Blocks

Page 18: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해Virtual Library

virtual library: computer simulated fitting of virtual molecules with the active site of the target enzyme

Novel compounds that bind to enzymes or receptors can be discovered by finding two fragments that bind and then synthetically combining

Page 19: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해Applications of Combinatorial Chemistry

Pharmaceutical industry: rapid synthesis of a huge number of drug-like molecules

Material science: new approach for the discovery of new materials

Catalyst discovery: fast discovery of new catalysts

Chemical biology: diversity-oriented synthesis of small organic molecules

Page 20: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해

Supramolecular ChemistrySupramolecular Chemistry

Page 21: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해

1. Molecular chemistry- Covalent bond

H2N NH2

O

150 years ago

urea

palytoxin

Page 22: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해초분자 화학

2. Supramolecular chemistry- Chemistry beyond moleculesAssembly of molecules – Molecular recognition

1987 노벨화학상 : 초분자화학Charles Pedersen, Jean-Marie Lehn, and Donald J. Cram

Non-covalent bonds: - electrostatic forces- hydrogen bonds- van der Waals interactions- dipole interactions- hydrophobic interactions, etc

Page 23: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해DNA and Hydrogen Bonds

N

N

NH2

R

N

NN

N

O

R

H

NH2N

N

N

N

O

O

H

R

NH2

O

R

thymine adenine

guanine cytosine

OBase

O

PO

O

O

Page 24: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해DNA and Hydrogen Bonds

NN

N

N

O

RH

NN

N

N

O RH

H

HH

NN

N

N

N

R

NN

N

O

O RH

H

HH

H

Which pair forms stronger hydrogen bonds? And Why?

-

+

+

+

-

-

+

-

+

-

+

-

Page 25: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해DNA and Hydrogen Bonds

3.9x108 M-1 3.6x106 M-1 3.3x104 M-1 3.3x104 M-1 3.1x102M-13.6x106 M-1

++++

----

+++-

---+

++-+

--+-

+--+

-++-

+-+-

-+-+

++--

--++

N

NN

H

R

O

H

N

O

H

N

NN

H

R

O

H

N

O

H

2

N

N N

H

R

O

H

N

O

H

Page 26: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해New Materials Based on Hydrogen Bonds

N

N N

H

R

O

H

N

O

H

N

NN

H

R

O

H

N

O

H

N

N N

HR

OH

N

O

HN

NN

HR

OH

N

O

H

N

N N

HR

OH

N

O

HN

NN

HR

OH

N

O

H

N

N N

HR

OH

N

O

HN

NN

HR

OH

N

O

H

N

N N

HR

OH

N

O

H

n

Page 27: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해Crown Ethers

18-crown-6 15-crown-5

O

O O

O

O O

O

O O

O

O

Na+K+

O

O

O

O

N

O

N

O

O OOOO O

K+K+

Cryptand

- 11 kcal/ mol - 18 kcal/ mol

Crown ether

NO

O

N

ON

CH3

CH3

H3C

N+

H

H H

R

Page 28: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해

W.C. Still D.J. Cram

Preorganized Ionophores

O

O

O

OO

O

K+

OO

O

O O

OH H

H HK+

OO

O

OOO

OOMe

O

OOOMe

MeMe MeMe

Preorganization: both binding affinity and selectivity are considerably increased

Page 29: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해Anion Recognition

Page 30: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해Anion Recognition

Page 31: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해Chemosensors

Signals:- fluorescence- color- electric signal...

Page 32: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해Chemosensors

ONH

N

CH3H3CN N

OHN

Hg(OAc)2

ONH

NH

CH3H3CN

NH

OS

NH

Hg(ClO4)2, CH3CN(98%)

H2O-MeOH(4 : 1)

1 only Hg2+ Ag+ Cu2+ Cd2+ Pb2+ Zn2+

Page 33: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해Carcerand

O

O

+ CO2

Page 34: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해

Molecular MachineMolecular Machine

Page 35: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해생체 분자기계

ATP Synthase

Bacterial Flagellar Motor

Linear movement - muscle(myosin moving along an actin filament)

Page 36: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해Interlocked Molecules

RotaxaneRota (wheel) + axis (axle)

CatenaneCatena (chain)

Page 37: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해분자 셔틀 버스 이동

Page 38: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해인공 분자기계

A catenane-based switching device for electric circuits.

Page 39: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해인공 분자기계

Catenane-based molecular rotor. A unidirectional rotation of the small rings along the large ring is achieved by their sequential complexation and decomplexation with four station parts A-D on exposure to light, heat, and chemical stimuli.

Page 40: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해분자 근육

Page 41: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해분자 엘리베이터

Page 42: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해분자 가위

Page 43: 첨단화학의 이해 Synthesis Make me a molecule Biology Materials Chemistry

첨단화학의 이해인공 분자기계

Chiral molecular motor composed of a tetrasubstituted alkene. Photoinduced and thermal-induced unidirectional rotation.