CH4049

Polymer Science
Application- Hydrogel/Aerogel

Dr. Po-Jung Huang

Department of Chemical and Materials Engineering, College of Engineering,
National Central University
Hydrogel

• A hydrogel is a crosslinked hydrophilic

polymer that does not dissolve in water.
• Hydrogel are highly absorbent yet maintain
well defined structures.
Use PEGDA As Material
Polyethylene (glycol) Diacrylate , PEGDA

UV Exposure
3D printer
Particle replication in nonwetting
templates (PRINT)
Structure of Hydrogel NH2 NH2 NH2 NH2

functional polymer chain

H 2N
O NH2 H 2N NH2
O
HN NH

cross-linker Working Region

HN NH

H 2N O
NH2 O H 2N

functional polymer chain

NH2 NH2
NH2 H 2N H 2N
Application

NO2- 、NO3- NH4+

NO3-
NO2-

NO3-

regeneration
photo-
NO2- decomposition
visible light responsive
N2 photocatalyst
 (a) Fabrication of functionalized PEGDA sorbents

precursor

photo-cross linking

3D printed mold patterned cubic wells functionalized PEGDA

(b) Treatments of nitrite, nitrate, and ammonium

Reusable hydrogel
NO2-, NO3- desorption
functionalized PEGDA
Resource hydrogel
NH4+ baking

Photocatalystic hydrogel
NO2- decomposition
Reusable Hydrogel PEGDA
PEGDA-NH2-NO3
PEGDA-NH2 PEGDA-NH2-NO2 PEGDA
PEGDA-MTAC-NO3
PEGDA-MTAC PEGDA-MTAC-NO2

NO3/NO2

NH3

Transmittance (%)
Transmittance (%)
CH3 NO3/NO2

N CH3

CH3 NH2 N-CH3

N-O N-O
NO2 NO2
4000 3500 3000 2000 1500 1000 500 4000 3500 3000 2000 1500 1000 500
Wavenumber (cm-1) Wavenumber (cm-1)
desorption

Sorption Capacity(mg NO3 -N /g sorbent)

Sorption Capacity(mg NO2 -N /g sorbent)
10 10 PEGDA-MTAC 1:1.5
PEGDA-MTAC 1:1.5
9 PEGDA-NH2 1:1.5
9 PEGDA-NH2 1:1.5
8 8
NO3/NO2 7
7

-
-
6 6
NH3 5 5
4 4
3 3
2 2
N
1 1
Cl 0 0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
cycle cycle

remaining sorption capacity: 70~80%

 Resource Hydrogel
Saturation: 30 min

adsorption

30
Langmuir-Freundlich isotherm
1:5 (Sips isotherm)
sorption capacity (mg NH4 /g sorbent)

5 3SMP 1:5 LFmodel (User) Fit of B

25
4 𝑄𝑠𝑎𝑡 (𝐾𝐶𝑒𝑞 )𝑛
𝑞=
Adsorption(mg/g)

20
+

3 1 + (𝐾𝐶𝑒𝑞 )𝑛
15
2
saturation 3SMP(1:5) /TiO2
10
1 Equation q =Qsat*(K*c)^n/((1+K*c)^n)
R-Square 0.99955
Adj. R-Square 0.99955
Value Standard Error

5
26.81±0.80 mg NH4+ / g sorbent
B Qsat 26.81168 0.80108
0 B
B
K
n
0.03059
0.59689
0.00342
0.01759
Qsat
0 5 10 15 20 25 30 0 10 20 30 40 50 60 70 80
K 0.031 ± 0.003
Time (min) Concentration(ppm)
n 0.59 ± 0.01
 Photo-degradation of Methylene Blue
First-order model : 𝒍𝒏 𝑪 = 𝒍𝒏 𝑪𝟎 − 𝒌𝒂 × 𝒕
LED
UV Material R2 ka （hour-1） Light
5
3-SMP（1：3）/N-TiO2 0.98208 0.25308 UV

4 3-SMP（1：5）/N-TiO2 0.95970 0.33613 UV

3 3-SMP（1：7）/N-TiO2 0.97712 0.38376 UV

-ln(C/C0)

2 3-SMP（1：3）/N-TiO2 0.99661 0.45502 LED

1 3SMP (1:3) /TiO2 3-SMP（1：5）/N-TiO2 0.99559 0.44849 LED

3SMP (1:5) /TiO2
3SMP (1:7) /TiO2 3-SMP（1：7）/N-TiO2 0.99520 0.57835 LED
0

0 0 2 2 4 4 6 6 8 8
10
Time (hour)
 Photocatalytic Hydrogel

selective adsorption
NO3-

H2S → V-shaped molecule

NO2-
3.661Å
graphene
Superlattices and Microstructures 134 (2019) 106235
orption Capacity (mg NO2- (or NO3-) / g sorbent)

22

Sorption Capacity (mg NO2- / g sorbent)

8 8 20 Graphene/TiO2=0.166/1
Graphene/TiO2=0.125/1 Graphene/TiO2=0.125/1
18
6 6 16
14
12 Graphene/TiO2=0.142/1
4 - - 4

qe
NO2 NO3 10
8
2 2 6
Graphene/TiO2=0.125/1
4
0 0 2
0 20 40 60 80 100 0 5 10 15 20 25 0 10 20 30 40 50 60 70 80 90 100
Concentration (ppm) Ce
Time (hour)
Photo-catalytic Hydrogel

Ref: Journal of Environmental Chemical Engineering

Volume 10, Issue 1, February 2022, 106902
Chelated Hydrogel
• Chelation is a type of bonding of ions and molecules to metal ions.
• Chelation involves the formation or presence of two or more separate coordinate
bonds between a polydentate (multiple bonded) ligand and a single central metal
atom.
Hard-Soft-Acid-Base

Atomic radius is large Atomic radius is small

Soft Acid Hard Acid
Cu+, Ag+, Au+, Pd2+, Li+, Na+, K+, Mg2+, Ca2+,
Hg2+, Pt2+, Cd2+ Al3+, Be2+
Soft Base Hard Base
CN-, SCN-, R2S F-, OH-, NH3, R-COOH
Effect of pH on adsorption capacity
(𝐏𝐝𝐂𝐥𝟒 )𝟐−
(𝐏𝐝𝐂𝐥𝟒 )𝟐−
S
S
140 (𝐏𝐝𝐂𝐥𝟒 )𝟐−
(𝐏𝐝𝐂𝐥𝟒 )𝟐− Ag(I)
(𝐏𝐝𝐂𝐥𝟒 )𝟐− Pd(II)

Qe ( mg M / g PEGDAATU )
120 +
H
N +
N
H
+ + 2 2
H
N
2 N
H
2
100 𝐏𝐝𝐂𝐥𝟒 )𝟐−
(𝐏𝐝𝐂𝐥𝟒 )𝟐− Ag(NO3)𝟐− Major Ag+
80 Ag+ Minor Ag+
Ionic interaction Ag(NO3)𝟐− Chelation
𝐀𝐠 + 60 𝐀𝐠 +
S
+

S
40 𝐀𝐠 +
𝐀𝐠 +
+
H
N +
N
H
2 2 20 +
H
N
2
+
N
H
2

𝐀𝐠(𝐍𝐎𝟑 )−
𝟐 -1 0 1 2 3 4 5 6
−
𝐀𝐠(𝐍𝐎𝟑 )𝟐 pH

Ionic interaction Fig 6. Effect of different pH on adsorption of Ag(I) and Pd(II). Chelation
where: C0=100ppm, W=5mg, V=10mL, 25℃.
Ref: Scientific Report, 11 (1), 1-12 15
FT-IR analysis 𝐍𝐎−
𝟑

pH = 1 1384
100
Ag(I)
Ag(NO3)𝟐− Major Ag+
Qe ( mg M / g PEGDAATU )

80 Ag+ Minor Ag(NO3)𝟐−

60
pH = 3

40
+

20 pH = 5

-1 0 1 2 3 4 5 6
pH

Fig 7. Effect of different pH on adsorption of Ag(I). 3500 2000 1500 1000 500
where: C0=100ppm, W=5mg, V=10mL, 25℃.
WaveNumbers (cm-1)
16
 Effect of contact time
Ag(I)
120 Adsorption
Ag(I)
Pd(II)
100
Qe (mg M /g sorbent)

300 minutes 20～80% 80～100%

80

60
+

40

20 Hydrogel sorbent

0
Pd(II)
0 60 120 180 240 300 360 Adsorption
Contact time (minutes)
Fig 8. Effect of different contact time on adsorption of Ag(I) 20～80% 80～100%
and Pd(II). where: C0=100ppm, W=250mg, V=500mL,
pH=1, 25℃.
17
Enzyme Immobilized Hydrogel
• Immobilized enzymes are very important for commercial uses as they possess
many benefits to the expenses and processes of the reaction of which include:
1. Convenience; 2. Economy; 3. Stability.

Immobilized enzymes Strategy:

• Adsorption
• Entrapment/Encapsulation
• Covalent Bonding
• Cross-linking
 實際圖

particles
material + enzyme

oil
 velocity ratio
Hydrogel Fabricated through 3:1
(O:W)
5:1 7:1
Microfluidic System

0.5 %
1000
velocity ratio 3:1
velocity ratio 5:1
800 velocity ratio 7:1

1.0 %
Surfactant Concentration
Hydrogel diameter(m)

600

1.5 %
400

200

2.0 %
0
0.5% 1% 1.5% 2%
Concentration of surfactant(%)
Laccase
• Laccases are multi-copper oxidases
found in plants, fungi, and bacteria.
• Laccases oxidize a variety of phenolic
substrates, performing one-electron
oxidations, leading to crosslinking.
• The active site consists of four copper
centers, which adopt structures
classified as type I, type II, and type III.
A tricopper ensemble contains types II
and III copper. It is this center that
binds O2 and reduces it to water.
 CR(pH=4)
2.0 1hr

Laccase-mediator system(LMS) 1.5

2hr
3hr
4hr
5hr

Absorbance
6hr
7hr
1.0 8hr
9hr
10hr

0.5

0.0

200 300 400 500 600 700 800

Wavelength(nm)

Acetosyringone Syringaldehyde
(乙醯丁香酮) (丁香醛)
p-Coumaric acid Cinnamic acid
(對香豆酸) (肉桂酸 )
100 100 100 100
p-Coumaric acid 0.1 mM Cinnamic acid 0.1 mM Acetosyringone 0.1 mM Syringaldehyde 0.1 mM
90 p-Coumaric acid 0.5 mM 90 Cinnamic acid 0.5 mM 90 Acetosyringone 0.5 mM 90 Syringaldehyde 0.5 mM
p-Coumaric acid 1.0 mM Cinnamic acid 1.0 mM Acetosyringone 1.0 mM Syringaldehyde 1.0 mM
80 p-Coumaric acid 2.0 mM 80 Cinnamic acid 2.0 mM 80 Acetosyringone 2.0 mM 80 Syringaldehyde 2.0 mM
70 70 70 70
Removal rate(%)

Removal rate(%)

Removal rate(%)
Removal rate(%)

60 60 60 60

50 50 50 50

40 40 40 40

30 30 30 30
20 20 20 20
10 10 10 10
0 0 0 0
0 1 2 3 4 5 6 7 8 9 10 0 1 2 3 4 5 6 7 8 9 10 0 1 2 3 4 5 6 7 8 9 10 0 1 2 3 4 5 6 7 8 9 10

Time(hour) Time(hour) Time(hour) Time(hour)

Metallic Catalyst Hydrogel
 Metallic Catalyst Hydrogel
Acidation Acidation Time
50 50

40 40

Conversion Rate (%)

Converison Rate (%)

30 30
Reusability
20
50
20

10 10 40

Conversion Rate (%)

0 0
Blank SMP-Na SMP-H 1hr 3hr 6hr 12hr 24hr
30
Type Acidation Time

GBL Concentration Metal ion 20

50 50

40 40 10
Conversion Rate (%)
Conversion Rate (%)

30 30
0
1st 2nd 3rd
20 20
Acidation Cycle

10 10

0 0
0.0 mL 1.5 mL 3.0 mL 4.5 mL H Na Cr Cu Co Ni Al Fe(II) Fe(III)
GBL amount Metal Ion
5-HMF Conversion Mechanism
Polymeric sorbents Polymeric photolytic catalyst

1. Surfactant
2. Nitrate/nitrite Nitrogen-Compound
3. Metal ion Degradation

Azo-dye
Degradation

Aromatic Pollutant
Degradation

5-HMF Conversion
Colloids and Surfaces A 577 (2019) 702–70
Nanoporous Structure – drying process
• Un-control drying (evaporation) → xerogel
• Supercritical drying → aerogel
• Freezing drying → cryogel
• Ambient drying→ ambigel

https://www.youtube.com/watch?v=kHnen2nSmDY
Cellulose Aerogel
Porous Cellulose Aerogels Process

BioRes. 11(1), 8-20

Lignin-based aerogel

Microporous and Mesoporous Materials 265 (2018) 258–265

Contraction of Cancer Cells- (a)
Based Microparticles
(b)
(c)

Normalizaion of Particles' Volume

1.0

0.8

0.6

0.4
1000 um collagen cube
0.2
500 um collagen cube
300 um collagen cube

0.0
0 1 2 3 4 5 6 7

Days
Cancer Model A. Classical orthotopic model

AsPC1/luc + Matrigel
B. PASMO based model
Pre-mix AsPc1/luc with matrigel
Form triangle shape
Mice xenograft tumor cell implantation Total flux (photon/sec, x105) Total flux (photon/sec, x105)
2
6

AsPC1 Luc cells + Matrigel Day 0

PASMO (Pancreatic cancer cells) 3 1

0 0
3 10

Day 7 2 5

0 0
Vevo 3100 high-
frequency micro-
ultrasound system

Matrigel + AsPC1 Luc cells Day 14

Tumor
volume 14.563 3.461 12.194 13.17
(mm3)
PASMO

PASMO based model has high tumorigenicity and lower variation than classical orthotopic model!
Artificial Islet Transplantation-subcutaneous transplantation

Artificial islet cluster Blood vessel