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Sensitive and highly selective determination of vitamin B1 in the presence of
other vitamin B complexes using functionalized gold nanoparticles as
fluorophore
Sekar Shankar and S. Abraham John*
Center for Nanoscience and NanotechnologyDepartment of Chemistry, Gandhigram Rural InstituteGandhigram – 624 302, Dindigul, Tamilnadu, India.
Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2015
OHS
NN
N
NH2
Thiamine Hydrochloride (Vitamin B1)
+
Cl-A N
NHS
OH
NH2
4-amino-6-hydroxy-2-mercapto pyrimidine (AHMP)
BA
N
HNN
NO
O
HO
OHHO
HO
Vitamin B2
CDBA
N
O
HO
Vitamin B3
DN
HO
OH
OH
Vitamin B6
E
O
HO
O
HO
O
HN
HN
N
N
N
N
OH
H2N
Vitamin B9
FBA
OO
HO
OH
OHHO
Vitamin C
G
Chart S1. Structures of AHMP and vitamin B complexes.
200 400 600 800
0
1
2
Abso
rban
ce
Wavelength (nm)
ab
c d
Fig. S1. Absorption spectra obtained for (a) AHMP, (b) HAuCl4 and after the addition (c) HAuCl4
to AHMP and (d) NaBH4 to a mixture of HAuCl4 and AHMP. Inset: Photograph of synthesized
AHMP-AuNPs .
Fig. S2. UV-visible (A) and emission spectra (B) of AHMP-AuNPs (λex: 520 nm; λem: 781 nm).
ABA
400 600 800
0
1
Abs
orba
nce
Wavelength (nm)
BA
760 780 8000
100
200
Inte
nsit
y
Wavelength (nm)
Fig. S3. UV-visible spectra of AHMP-AuNPs (a) freshly prepared, (b) after the three month. Inset:
Corresponding photographs of UV-visible spectra (a) freshly prepared, (b) after the five month.
400 600 800
0.5
1
Abs
orba
nce
Wavelength (nm)
b
a ba
A BA
.
Fig. S4. Zeta potential measurement of AHMP-AuNPs (A) before and (B) after the addition of
1.20 × 10-6 M thiamine.
40 60 802
Inte
nsity
(a.u
)
(111
)(2
00)
(220
) (311
)
Fig. S5. X-ray Diffraction pattern of AHMP-AuNPs.
400 600 800
0
1
a
m
Abs
orba
nce
Wavelength (nm)
Fig. S6. UV-vis spectra of AHMP-AuNPs in different concentrations of thiamine: (a) 0, (b)
0.15, (c) 0.30, (d) 0.45, (e) 0.60, (f) 0.75, (g) 0.90, (h) 1.05, (i) 1.20 , (j) 1.35, (k) 1.50, (l)
1.65 and (m) 1.80 × 10-6 M.
760 780 8000
100
200FL
inte
nsity
Wavelength (nm)
450
520 nm
600 nm
525
exci
tatio
n (e
x)
ex
Fig. S7. Emission spectra of AHMP-AuNPs by varying excitation wavelength from 450 -
600 nm (interval 5 nm).
-11.0 -10.8 -10.6 -10.4 -10.2 -10.0 -9.8
-1.0
-0.8
-0.6
-0.4
-0.2R2=0.9949y=7.7802+0.8034x
log
[F-F
0/F0]
log [Q]
Fig. S8. Plot for binding constant of AHMP-AuNPs with thiamine.
Table S1. DFT calculation of AHMP and AHMP-AuNPs
Compound HOMO LUMO
Energy
gap (eV)
AHMP 4.8731
AHMP-
AuNPs2.4990
Table S2. Comparison of thiamine limit of detection and linear range obtained in the present work
with reported methods
Methods Medium Linear rangeLimit of
detectionRef.
Spectrofluorimetry alkaline 1×10-4 - 1×10-8 M 4.3 nM L-1 2
Spectrofluorimetry water 3.3 µM – 8.3 nM 2.6 nM L-1 14
Spectrofluorimetry alkaline1.9×10-4 – 2.7×10-7
M5×10-8 M L-1 15
HPLC methonal5×10-7 M - 5×10-10
M1×10-10 M L-1 20
Capillary
electrophoresiswater Not reported 0.05 µg ml-1 23
Square wave
voltammetrywater 2.2 µM - 1×10-8 M 5.5 nM L-1 24
Chemiluminescence water 4×10-5 - 1×10-7 M 4.8 nM L-1 43
Spectrofluorimetry water 10 – 120 pM 6.8 fM L-1 present method
Table S3. Determination of thiamine in human blood serum samples (n=5)*
Samples thiamine spiked (ng L-1) thiamine found (ng L-1) RSD Recovery (%)
Sample 1 10 9.9 ± 0.1 0.55 99.4
Sample 2 20 19.9 ± 0.1 0.42 99.6
* Five replicate measurements