Synthesis of Amphiphilic Block Copolyamines via Click Reaction

Vanga Devendar Goud1, Roshan DSouza1, Suresh Valiyaveettil*Department of Chemistry, 3 Science Drive 3, National University of Singapore, Singapore 117543

SUPPLEMENTARY INFORMATION

Fig. S1. FTIR spectra of precursor polymer PES-b-PS (5), and target amine-functionalized block

copolymers P1 – P4 recorded using KBr as matrix.

1

Fig. S2. TGA curves of precursor polymer 5 and block copolymers P1 – P4 recorded under

nitrogen atmosphere.

Figure S3. DSC curves of block copolymers at N2 atmosphere using a heating rate of 10 ºC/min.

2

Figure S4. GPC curves indicating the formation of block polymers, poly[(trimethylsilyl)

ethynylstyrene] 2 and poly[styrene-b-(trimethylsilyl)ethynylstyrene] 4. The dotted line shows the

incomplete conversion of macroinitiator 2 during reaction process.

Figure S5. Pseudo-first order kinetics for the extraction of (A) Ag-Cit (B) Ag-PVP and (C) Au-

Cit and (D) Au-PVP NP’s from water by block copolymers at ambient conditions.

3

A B

C D

Table S1. Pseudo-first and second order constants and correlation coefficients for the extraction

of metal NP’s by polyamines, P1 – P4

NPs Polymers

Qe(exp)Pseudo-first order

kinetic model

Pseudo-second order

kinetic model

(mg/g)Qe

(mg/g)

K1

R2Qe

(mg/g)

K2

R2

  (min-1)(g/mg

min)

Ag-citrate

P1 34.22 15.91 0.0152 0.024 33.88 0.00383 0.929

P2 18.71 8.99 0.0790 0.751 19.15 0.02224 0.999

P3 18.68 13.11 0.0888 0.953 19.37 0.01453 0.998

P4 5.95 5.78 0.0306 0.865 7.36 0.00427 0.843

Ag-PVP

P1 12.17 4.40 0.0519 0.922 12.26 0.05117 0.999

P2 12.03 12.05 0.0308 0.981 13.48 0.00284 0.983

P3 19.81 15.63 0.0129 0.749 21.98 0.00175 0.852

P4 15.51 15.93 0.0651 0.974 17.50 0.00435 0.992

Au-citrate

P1 25.74 16.94 0.0523 0.798  27.03 0.00639 0.998

P2 25.74 21.06 0.0719  0.952 26.99 0.00745 0.999

P3 25.91 18.90 0.0647  0.953 26.94 0.00816 0.999

P4 12.38 11.37 0.0205  0.949 15.93 0.00159 0.928

Au-PVP

P1 13.19 3.90 0.0143 0.231 13.16 0.01439 0.965

P2 11.78 10.38 0.0465 0.858 12.97 0.00601 0.968

P3 7.02 5.27 0.0319 0.931 7.63 0.01097 0.996

P4 6.67 5.12 0.0164 0.78 7.42 0.00607 0.918

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Figure S6. Pseudo-first order kinetics for the extraction of (A) Lead and (B) Chromium from

water by block copolymers at ambient conditions.

Table S2. Pseudo-first order and pseudo-second order constants and correlation coefficients for

the extraction of lead and chromium ions using polyamines, P1 – P4.

Metal ions Polymers

Qe(exp)Pseudo-first order

kinetic model

Pseudo-second order

kinetic model

(mg/g)Qe

(mg/g)

K1

R2Qe

(mg/g)

K2

R2

  (min-1)(g/mg

min)

Lead

P14.98 2.60 0.0101 0.043 5.33

0.0053

30.983

P24.65 1.46 0.0055 0.254 4.69

0.0161

50.996

P34.39 2.58 0.0043 0.197 4.75

0.0031

20.949

P43.65 4.25 0.0222 0.781 4.32

0.0024

30.877

ChromiumP1

7.99 1.49 0.0244 0.365 8.010.2137

30.999

P28.91 3.84 0.0035 0.161 9.03

0.0040

80.983

P3 5.04 2.00 0.0044 0.241 5.10 0.0096 0.991

5

A B

0

P42.58 3.13 0.0606 0.976 2.69

0.0355

30.984

Figure S7. Pseudo-first order kinetics for the extraction of (A) neutral red and (B) brilliant blue

dyes by block copolymers from water at ambient conditions.

Table S3. Pseudo-first order and pseudo-second order constants and correlation coefficients for

the extraction of brilliant blue, and neutral red dyes by polyamines, P1 – P4

DyesPolymer

s

Qe(exp)Pseudo-first order kinetic

model

Pseudo-second order kinetic

model

(mg/g)Qe

(mg/g)

K1

R2Qe

(mg/g)

K2

R2

  (min-1)(g/mg

min)

BB

P1 20.83 8.94 0.0300 0.663 21.10 0.01194 0.999

P2 34.00 18.11 0.0530 0.942 34.29 0.01031 0.999

P3 34.64 10.57 0.0141 0.855 35.09 0.00556 0.999

P4 34.45 11.32 0.0096 0.487 34.67 0.00389 0.999

NR

P1 15.53 2.94 0.0076 0.095 15.51 0.01581 0.998

P2 15.91 1.59 0.0004 0.063 15.29 -0.06495 0.999

P3 18.71 2.71 0.0018 0.135 16.75 -0.03740 0.999

P4 18.11 5.10 0.0068 0.546 18.00 0.01087 0.999

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A B

Figure S8. UV-visible spectra of Au and Ag NPs in water.

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Figure S9. TEM images of Au and Ag NPs.

Table S4. Dynamic light scattering (DLS) for diameter and electrokinetic surface charge

measurement for PVP and citrate capped Au and Ag-nanoparticles.

Nanoparticle Size (nm) Zeta potential (mV)

Au – PVP 48.30 - 21.4

Ag – PVP 40.49 - 22.9

Au – Citrate 26.38 - 37.3

Ag – Citrate 60.33 - 40.3

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