Electronic Supplementary Material
Ultrasensitive Determination of Mercury (II) using Glass Nanopores Functionalized with
Macrocyclic Dioxotetraamines
Rui Gaoa, Yi-Lun Yinga*, Bing-Yong Yanb, Parvez Iqbalc, Jon A. Preecec and Xinyan Wua
a
Key Laboratory for Advanced Materials & Department of Chemistry, East China University of
Science and Technology, Shanghai 200237, P. R. China
b
School of Information Science and Engineering, East China University of Science and
Technology, Shanghai 200237, P. R. China
c
School of Chemistry, University of Birmingham, Edgbaston, Birmingham, B15 2TT , UK
* To whom correspondence should be addressed: yilunying@ecust.edu.cn
1.
Synthesis of C5
C5 were prepared via multistep synthetic routes. the naphthalimide derivative 3 (scheme S1) is an
integral component and the synthesis of this component was initiated by the synthesis of azide 1
via reacting the commercially available 11-bromoundecene with sodium azide at an alleviated
temperature. Azide 1 was reduced to alkylamine 2 in the presence of Zn and NH4Cl, which was
reacted with the commercially available 4-bromo-18-naphthalic anhydride at alleviated
temperature to give the desired naphthalimide derivative 3. The naphthalimide derivative 3 was
alkylated with ethanolamine to give the naphthalimide alcohol 4. The conversion of the alcohol to
bromine was achieved in the presence of triphenylphosphine and carbon tetrabromide to obtain
bromo-naphthalimide 5. Thioacetylation of bromo-naphthalimide 5 was performed under the
presence of thioacetic acid and catalytic amount of AIBN to give thioacetate 6. The macrocylic
dioxotetraamine was alkylated with thioacetate 6 to obtain the macrocycle thioacetate 7 and the
subsequent hydrolysis of thioacetate 7 in acidic conditions gave the desired molecule C5.
Macrocycle thioacetate 7: 1H NMR (300 MHz, CDCl3, Me4Si, 25 oC) δH ppm; 8.48-7.82 (m,
4H), 6.32 (br, 1H), 4.05-4.3.52 (m, 20H), 2.78 (t, 2H, J = 7.00 Hz), 2.42-3.32 (m, 8H), 2.25 (s,
3H), 1.89-1.72 (m, 2H), 1.67-1.62 (m, 2H), 1.51-1.45 (m, 4H), 1.43-1.20 (m, 14H); 13C NMR
(75 MHz, CDCl3, Me4Si, 25 oC) δC ppm 170.9, 164.4, 164.0, 148.0, 134.3, 131.1, 129.8, 125.8,
125.1, 123.3, 120.6, 111.7, 104.6, 53.0, 48.7, 47.0, 46.5, 44.8, 44.3, 42.0, 40.3, 38.2, 30.6, 29.3,
29.2, 29.1, 29.0, 28.8, 28.2, 28.0, 27.2; m/z (ESMS): 718 ([M + Na]+, 100%); m/z (HRMS):
found 717.9109. Calc. Mass for C35H52N6O4SNa:717.9166.
Molecule C5: m/z (ESMS): 676 ([M + Na]+, 100 %); m/z (HRMS): found 675.8732. Calc. Mass
for C35H52N6O4SNa: 675.8799.
Scheme S1. Synthesis of molecule C5; (i) NaN3, DMSO, reflux, 3h, 85 %; (ii) Zn/NH4Cl,
H2O:EtOH (1:1), reflux, 1 h, 91 %, (iii) EtOH, reflux, 16 h, 96 %; (iv) NH2(CH2)2OH,
MeO(CH2)2OH, reflux, 18 h, 90 %; (v) PPh3, CBr4, THF, rt, 16 h, 89 %; (vi) HSAc, AIBN,
PhMe, reflux, 2 h, 52 %; (vii) K2CO3, MeCN, N2(g) atm, reflux, 16 h, 24 %; (viii) 0.1 M HCl,
N2(g) atm, reflux, 4 h, 27 %.
Comparisons between nanopore-based methods for the detection of Hg2+
2.
Table S1. Features of recently reported nanopore-based methods for detection of Hg2+
Poreforming
materials
Strategy
LODs
General advantages
References
αHemolysin
Detection of
translocation
events1
7 nM
Design of an ssDNA
probe to detect Hg2+
1
αHemolysin
Detection of
translocation
events1
0.5 nM
Design of Hg2+-mediated
DNA duplex to
precluding background
interference
2
αHemolysin
Detection of
translocation
events1
25 nM
Design of the hairpins
with small loops to
improve the sensitivity2
3
Rectification
measurements
Rapid, high mechanical
stability, no requirements
~10 pM of probing DNA strands
and time-consuming
statistical analysis
Glass
pipette
1
This work
The formation of T-Hg2+-T regulated translocation events of the probe DNA strand. 2The hairpin
loop of the probe DNA strand contained the binding site for Hg2+.
3.
Reproducibility of C5-funtionalized glass nanopore
Fig S1. Reproducibility of C5-funtionalized glass nanopore for the detection of Hg2+. The
rectification ratio were obtained in a 10 mM KCl solution with 1 nM Hg2+ under the voltage of ±
500 mV.
Reference
1. Wen S, Zeng T, Liu L, Zhao K, Zhao Y, Liu X, Wu HC (2011) Highly sensitive and selective
DNA-based detection of mercury(II) with alpha-hemolysin nanopore. J Am Chem Soc
133:18312-18317.
2. Zeng T, Li T, Li YR, Liu L, Wang XY, Liu QS, Zhao YL, Wu HC (2014) DNA-based
detection of mercury( II ) ions through characteristic current signals in nanopores with high
sensitivity and selectivity. Nanoscale, 6:8579-8584.
3. Wang GH, Zhao QT, Kang XF, Guan XY (2013) Probing Mercury (II) − DNA Interactions by
Nanopore Stochastic Sensing. J. Phys. Chem. B, 117: 4763-4769.