1. Kontroll Radikal Polimerizasyonu RAFT 2.

Bakteriyel Selloz Nanofiberler

Kontroll radikal polimerizasyonu

iPOx (2-isopropenyl-2-oxazoline) un RAFT (reversible addition-fragmentation chain transfer) polimerizasyonu Asit modifikasyonu ve LCST al malar

Jena,Almanya

Kontroll radikal polimerizasyonu (CRP) vs. Serbest radikal polimerizasyonu (RP)

RP de ba lama yava t r. CRP de ba lama ok h zl d r. Tm zincirlerin anl k bymesi grlr. CRP de l zincir oran yakla k < %10 dur.

RP de nerdeyse tm zincirler ldr.

RP nin polimerizasyon h z yksektir.

CRP nin polimerizasyon h z yava t r.

RP de sonlanma genelde uzun zincirler aras nda olur.

CRP de btn zincirler reaksiyonun erken safhalar nda k sad r, zincir uzunlu u zamanla byr.

PDI (poly dispersity index): proteinler ve aminoasitlerin 1.0; serbest radikal polimerizasyonu ile haz rlanan polimerlein 2.0 ve st; RAFT ile sentezlenenlerin 2.0 nin alt ndad r.

RAFT n al ma mekanizmas

RAFT ile neler yapabiliriz?

Parametreler

RAFT Ajanlar CTA1, CTA4, CTA5, CTA6, CTA8, CTA9,CPDB

zcler Etanol, Toluene

S cakl k 60C, 70C, 80C

Zincir Transfer Ajan /Ba lat c 4 ve 10

RAFT ajan seimi

RAFT Agents
1.0 0.8 0.6 0.4 0.2 0.0 6 7 8 9 10 11 12 13
CPDB CTA4 CTA9 CTA6 CTA5 CTA8

Normalized RI Signal

Elution Volume in mL

Table 1. Properties of the piPOx with deifferent RAFT agents

CTA CPDB CPDB CPDB CTA4 CTA5 CTA6 CTA8 CTA9 CTA9 Conversion 17 60 23 29 30 31 21 22 21 Solvent Toluene Ethanol Toluene Toluene Toluene Toluene DMF Toluene Ethanol Mn 3300 3160 2100 5420 365 6100 2640 6100 2000 PDI 1.36 2.1 1.6 1.7 1.56 1.66 2.3 1.8 8.4 Temperature (C) 70 70 60 70 70 70 70 70 70

PDI ve Mw : SEC (size exclusion chromatography) Dn m: H-NMR

SEC-1(CHCl3, PMMA Calibration)

Reaction time is 24 h for all experiments

Reaksiyon ko ullar n n optimizasyonu

1.0 0.8 0.6 0.4 0.2 0.0 5 6 7 8 9 10 11 12
Ethanol Toluene

1.0 0.8 0.6 0.4 0.2 0.0 5 6 7 8 9 10 11

Ethanol Toluene

Normalized RI Signal

Normalized RI signal

12

Elution Volume in mL

Elution volume in mL

Figure 1. SEC trace of different solvents. RAFT agent: CPDB, M/CTA:100, 70C, reaction time:18h

zc: Toluene Raft agent: CPDB M/CTA: 50 CTA/AIBN: 10 S cakl k: 60 C

Figure 2. SEC trace of different solvents. RAFT agent: CPDB, M/CTA:50, 70C, reaction time:18h
0

60 C,36h 0 70 C,18h

1.0

1.0
CTA/AIBN.10 CTA/AIBN.4

0.8

Norm alized RI S ignal

0.8 0.6 0.4 0.2 0.0

Normalized RI Signal

0.6

0.4

0.2

0.0

10

11

12

10

11

12

Elution Volume in mL

Elution Volume in mL

Figure 3. SEC trace of different AIBN ratio. RAFT agent:CPDB, M/CTA: 50, 60C, reaction time: 96h

Figure 4. SEC trace of different temperature. RAFT agent: CPDB, M/CTA:50

SEC-1(CHCl3, PMMA Calibration)

piPOx, 1H-NMR and SEC-1

CHCl3

piPOX
2 1 -N-CH2 -O-CH2

3 -CH3 -CH2

1.0

piPOx
0.8

Normalized RI Signal

0.6

0.4

6
3

4 ppm

0.2

0.0

10

11

12

Elution Volume in mL

PDI : 1.38 Mn : 2400 g/mol

1
2

1H NMR

(CDCl3, 250MHz)

SEC-1(CHCl3, PMMA Calibration)

Modifikasyon
Reaksiyon ko ullar : Solvent: DMF S cakl k: 60 C Tepkime sresi: 24 sa

Kullan lan asitler

1.0

0.8

Ace.ac.react. Benz.ac.react. Butyr.ac.react. Prop.ac.react. piPOx

Normalized RI Signal

0.6

0.4

0.2

Ac.ac.react.
0.0

Benz.ac.react.

10

11

12

Elution Volume in mL

Buty.ac.react. Prop.ac.react.
8 6 ppm 4 2 0

Name of acid Acetic acid Benzoic acid Butyric acid Propionic acid

Mn (g/mol) 5200 3000 3000 2700

PDI 1.26 1.37 1.36 1.25

Conversion 35 100 19 17

LCST (lower critical solution temperature)

1H-NMR (CDCl , 3

250MHz)

SEC-1 (CHCl3, PMMA calibration)

Tiyofenol reaksiyonu
piPOx thiophenol reacted polymer
1.0

0.8

Normalized RI signal

0.6

0.4

0.2

0.0

8.5

9.0

9.5

10.0

10.5

11.0

11.5

12.0

12.5

thiophenol reacted polymer

Elution volume in mL

PDI =1.22, Mn = 1400g/mol

piPOx

ppm

1H-NMR (CDCl , 3

250MHz)

SEC-1 (CHCl3, PMMA calibration)

Benzoik asit ile modifiye edilmi piPOx

1.0

benz.ac.react.piPOx piPOx

0.8

Normalized RI Signal

0.6

0.4

0.2

0.0

10

11

12

Elution Volume in mL

Mn : 3800 g/mole
benz. ac. react. piPOx

PDI : 1.33

piPOx
8 6
ppm

1H NMR

(CDCl3, 250 MHz)

SEC-1( CHCl3, PMMA Calibration)

RAFT n MIP uygulamalar

Geleneksel radikal polimerizasyon ile sentezlenen polimerlerin zincir byme h z kontrol edilemez, yan tepkimelerden dolay genellikle geni boyut da l m na sahiptirler. Bu sorunu zmek ad na MIP sentezinde RAFT kullan labilir. RAFT ajan n n varl nda elde edilen polimerlerin dar boyut da l m grlr.

Monomer: MAA apraz ba lay c : EDMA Ba lat c : AIBN RAFT ajan : DBTTC zc: dodecanol S cakl k: 60 C Sre: 24 sa Kal p molekl: Enrofloxacin

MIP lerin hepsi NIP lerden daha yksek afinite gstermi tir. Yksek yzey alan na sahip M6 ve M7 ysek resolsyon gstermi tir.

Molekler bask lanm bakteriyel selloz nanofiberler

Nanofiber: Fiber ap 1 mden kk malzemelere denir. Kromatografi malzemesi olarak geleneksel kolon malzemelerine kar baz avantajlar vard r: d k bas n kayb d k difzyon direnci yksek yzey alan

Bakteriyel selloz
Yap s :

Kullan m alanlar :

BS nin retimi

Acetobacter xylinum ATCC 10245

Durgun Kltr

alkalamal Kltr

Nanofiberler ile molekler bask lama stratejileri

Dinledi iniz iin te ekkr ederim