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Electronic Supplementary Material
Synthesis of Organic Motif Tailored Hybrid Nanoframes: Exploiting in vitro Bioactivity
and Heavy Metal Ion Extraction Applications
Kundan C. Tayade†, Sopan T. Ingle†, Anil S. Kuwar‡, Sanjay B. Attarde†*
†School of Environmental and Earth Sciences, North Maharashtra University, Jalgaon (MS) India.
‡ School of Chemical Sciences, North Maharashtra University, Jalgaon (MS) India.*E-mail- : [email protected]
_____________________________________________________________________________________
4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 450.01.4
4
6
8
10
12
14
16
18
20
22
24
26
28
30
32
34
36
38
39.1
cm-1
%T
3301.15
2924.20
2854.23
1635.15
1598.16
1518.77
1463.43
1416.891363.19
1296.59
1247.54
1174.02
1133.66
1052.69
1005.61
955.79
906.69
823.72
787.14
694.63
592.81
565.64
501.96
1681.38
1666.31
3196.54
3140.38
Fig. S1. FTIR spectrum of the synthesized abiotic motif L.
4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 450.05.7
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30.0
cm-1
%T
3388.92
2924.19
2854.08
1630.84
1461.11
1377.31
589.51
1031.251121.66
1156.11
1280.971741.66
630.83
4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 450.05.2
6
8
10
12
14
16
18
20
22
24
26
28
30
32
34
36
38
40
42
43.8
cm-1
%T
3410.24
2923.69
2854.11
1635.00
1462.58
1377.29
1092.16
721.53
583.94
805.20
469.37
970.97
IR spectrum of Fe3O4 NPs, recorded in nujol
IR spectrum of Fe3O4@SiO2 NPs, recorded in nujol
4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 450.05.8
8
10
12
14
16
18
20
22
24
26
28
30
32
34
36
38
39.9
cm-1
%T
3384.61
2854.09
1624.78
1460.37
1377.28
1100.00
793.29
721.73
569.48
473.70
2099.35
964.51
1308.95
2730.02
628.68
Fig. S2. FTIR spectra of the synthesized pristine and modified NPs in Nujol (Because of basic
peaks of nujol intensity of rest of the peaks get affected)
5007501000125015001750200025003000350040001/cm
0
10
20
30
40
50
60
70
80
90
100
%T
Sio2 MNP
Characteristic IR peaks for SiO2
IR spectrum of Fe3O4@SiO2@L NPs, recorded in nujol
IR spectrum of Fe3O4@SiO2 NPs, recorded in KBr
Peak ≈ 1550 cm-1
NH (amide II band) bending
5007501000125015001750200025003000350040001/cm
0
10
20
30
40
50
60
70
80
90
100
%T
S8MNP
Fig. S3. FTIR spectra of the synthesized Fe3O4@SiO2 NPs and Fe3O4@SiO2@L NPs in KB
Table ST1- Comparison of fundamental FTIR frequencies of Fe3O4, Fe3O4@SiO2 NPs with literature reported values and FTIR values of Fe3O4@SiO2@L
IR frequency description (cm-1)
Literature reported method
Present method
Fe3O4 Fe3O4@SiO2 Fe3O4 Fe3O4@SiO2 Fe3O4@SiO2@LH–O–H stretching modes (free or adsorbed water)
3380 (cm-1)
3428 (cm-1)
3389 (cm-1)
3310 (cm-1)
3385 (cm-1)
H–O–H bending vibration (free or adsorbed water)
1630 (cm-1)
1640 (cm-1)
1631 (cm-1)
1635 (cm-1)
1625 (cm-1)
Fe–O bending 582 (cm-1)
--589
(cm-1)-- --
Si–O–Si antisymmetricalStretch (Broad)(←Si-O→←Si)
--1080 (cm-1)
--1092 (cm-1)
1100 (cm-1)
Si–O–Sisymmetric stretch(←Si-O-Si→)
--798
(cm-1)--
805 (cm-1)
793 (cm-1)
Si–O–Fe--
574 (cm-1)
--584
(cm-1)569
(cm-1)Si–OH
--965
(cm-1)--
971 (cm-1)
965 (cm-1)
IR spectrum of Fe3O4@SiO2@L NPs, recorded in KBr
Peak ≈ 1550 cm-1
NH (amide II band) bending
200 400 600 800 1000 1200 1400 1600 1800 20000
0.10.20.30.40.50.60.70.8
Raman Shift (cm-1)
Inte
nsity
(a.u
.)-C-N-Stretch
-CH2-Stretch
-NH-C=OStretch
-C-C-Stretch
Fig. S4. Raman spectra of the synthesized key NPs
Fig. S5. EDX image of the pristine Fe3O4 NPs
Fig. S8. TEM image of Fe3O4@SiO2 NPs, reveals the aggregation of pristine Fe3O4 NPs (core) in SiO2 shell.
Fig. S9. Particle size analysis of Fe3O4@SiO2@ L NPs (hybrid NPs)
0 50 100 150 200 250 300 3500.00E+00
5.00E-03
1.00E-02
1.50E-02
2.00E-02
2.50E-02
3.00E-02Fe3O4 NPs Fe3O4@SiO2 NPs Fe3O4@SiO2@L NPs
Diameter [Å]
Dv(
d)[
cc/Å
/g]
Fig. S10. BJH plots of the synthesized NPs
0 50 100 150 200 250 300 350 4000.00E+00
5.00E-03
1.00E-02
1.50E-02
2.00E-02
2.50E-02
3.00E-02
Fe3O4 NCs Fe3O4@SiO2 NCsFe3O4@SiO2@L NCs
Pore Width (Å)
dV
(w)[
cc/Å
/g]
Fig. S11. DFT plots of the synthesized NPs
3 3.5 4 4.5 5 5.50
20406080
100120140160180
f(x) = 7.45714053367441 x − 4.52128690753276R² = 0.999609800149795
f(x) = 31.2825153558648 x + 3.50815298815675R² = 0.998696941092322
f(x) = 8.30977434569621 x − 6.30998753532353R² = 0.984903879431731
Fe3O4 NPs Linear (Fe3O4 NPs)
Thickness (t), in [Å]
Volu
me
Adso
rbre
d, in
[cc/
g]
Fig. S12. T-plots of the synthesized NPs
Table ST2. DFT observed parameters of the synthesized NPs
Sr. No. Code Pore volume (cc g-1)
Lower confidence limits (nm)
Actual Fitting Error (%)
pore width (mode)(Å)
1. Pristine Fe3O4 NPs 0.7944 1.6137 2.630 3.6000×1002
2. Fe3O4@SiO2 NPs 0.5584 1.6879 0.574 3.7943×1001
3. Fe3O4@SiO2@L NPs 0.9269 1.6879 3.524 2.8746×1002
Table ST3.Table depicting summary of an assortment of parameters derived from the magnetization curve
Sample Mass, gAverage Time, sec
Time Constant, sec
Sensitivity, emu
Number of points
Magnetization (Ms), emu
Coercivity (Hci), G
Retentivity (Mr), emu
PrestineFe3O4
NPs
4.90×10-02 3 1 -6.1 151 1.5266 15.467 2.24×10-02
F
e3O4@SiO2@L
NPs
34.00×10-03 3 1 -17 151 1.1744 28.573 37.06×10-03
Fig. S13. TGA of organic motif L recorded at heating rate of 5 oC/min
Table ST4. Computed RL values for Zn(II) ion sorption
Concentration (ppm) RL
Concentration (ppm) RL
1 0.869 750.08
1
2.5 0.727 1000.06
2
5 0.571 1500.04
2
12.5 0.347 2500.02
6
25 0.210 4000.01
6
37.5 0.151 5000.01
350 0.117
Table ST4. Comparison of literature reported work with current work
Working Group
Material Used for Extraction
Material Origin and Magnetism
Langmuir Isotherm
Present Study
Fe3O4@SiO2@(L) NPs Synthetic Materials, Magnetic
Qm (mg/g) b (L/mg) RL R2
158.73 0.150 0.268 0.9993
Freundlich Isotherm Temkin Isotherm
1/n n KF
(mg/g) R2 A
(L/mg)b
(KJ/mol)B R2
0.5158 1.9390 37.3150 0.9797 1.42E-03 0.1054 105.43 0.9836Dada et
al.[1]
Rice husk modified with orthophosphoric acid
Biosorbent,Nonmagnetic
Langmuir Isotherm
Qm (mg/g) b (L/mg) RL R2
101.01 0.065 0.133 0.9900
Freundlich Isotherm Temkin Isotherm
1/n n KF
(mg/g) R2 A
(L/mg)b
(KJ/mol)B R2
0.625 1.6 7.61 0.89 1.075 97.788 2 5.34 0.6 1 5 Amini et
al.[2]
Fe3O4@SiO2
NanoparticlesSynthetic Materials, Magnetic
Langmuir IsothermQm (mg/g) b (L/mg) RL R2
119 0.1356 -- 0.997
Freundlich Isotherm Temkin Isotherm1/n n KF
(mg/g) R2 A
(L/mg)b
(KJ/mol)B R2
0.663 -- 13.09 0.975 -- -- -- --
References:
1. A.O. Dada, A.P. Olalekan, A.M. Olatunya, O. Dada, Langmuir, Freundlich, Temkin and
Dubinin–Radushkevich Isotherms Studies of Equilibrium Sorption of Zn2+ Unto Phosphoric Acid
Modified Rice Husk, IOSR Journal of Applied Chemistry, 2012, 3, 38–45.
2. Masoomeh Emadi, Esmaeil Shams, Mohammad Kazem Amini, Removal of Zinc from
Aqueous Solutions by Magnetite Silica Core-Shell Nanoparticles, Journal of Chemistry, 2013,
http://dx.doi.org/10.1155/2013/787682.