electronic supporting information · s15 figure ss12: fluorescent titration of fq1 (20 μm in...
TRANSCRIPT
S1
Electronic Supporting Information
Rational designing of first furoquinolinol based molecular systems for easy detection of
Cu2+ with potential applications in the area of membrane sensing
Manoj Kumar,a,‡ Lokesh Kumar Kumawat,a,‡ Vinod Kumar Guptaa,b and Anuj Sharmaa,*
aDepartment of Chemistry, Indian Institute of Technology Roorkee, Roorkee-247667, India
bDepartment of Applied Chemistry, University of Johannesburg, Johannesburg, South-Africa
*Corresponding author
Phone: +9113 3228 4751
Fax: +9113 3227 3560
e-mail: [email protected], [email protected]
‡Contributed equally as co-first authors.
Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2015
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Title Page..............................................................................................S1
Content Page........................................................................................S2
Analytical data......................................................................................S3
Spectra, Figures, Tables..................................................................S4-S30
S3
Analytical data
3-(4-bromophenyl)-2-((2-morpholinoethyl)amino)furo[3,2-c]quinolin-4-ol (FQ1).
Yellow solid (81%), mp (decomp.) = 258-259°C, IR (KBr, cm-1): ʋmax = 3369, 2963, 2864, 2821, 1655, 1602, 1498. 1H NMR (400 MHz,
CDCl3): δH = 2.47 (br s, 4H), 2.61 (br s, 2H), 3.48 (br s, 2H), 3.66 (br s, 4H), 5.26 (br s, 1H), 7.21–7.29 (m, 3H)*, 7.38 (td, 1H, J = 7.3 & 1.2
Hz), 7.54 (s, 4H), 7.82 (d, 1H, J = 7.8 Hz), 10.49 (s, 1H). 13C NMR (100 MHz, CDCl3): δc = 37.2, 48.5, 52.8, 62.2, 89.9, 103.3, 106.0, 115.1,
117.7, 120.0, 123.6, 125.9, 126.6, 128.5, 130.4, 141.0, 155.0, 155.4, 160.8. HRMS (ESI) m/z calcd. for C23H22BrN3O3 [M-H]+ : 466.0760,
found: 466.0765.
3-(4-chlorophenyl)-2-(pentylamino)furo[3,2-c]quinolin-4-ol (FQ2).
Yellow solid (78%), mp = 218-220 °C, IR (KBr, cm-1): ʋmax = 2827, 1661, 1606, 1500, 1416. 1H NMR (400 MHz, CDCl3): δH = 0.87–0.94 (m,
3H), 1.36 (m, 4H), 1.64 (quint, 2H, J = 7.2 Hz), 3.39 (t, 2H, J = 7.1 Hz), 4.38 (br s, 1H), 7.14–7.26 (m, 2H)*, 7.32 (m, 2H), 7.39 (d, 2H, J = 8.5),
7.58 (dt, 2H, J = 8.5 & 1.8 Hz), 7.82 (d, 1H, J = 7.8 Hz), 11.17 (s, 1H). 13C NMR (100 MHz, CDCl3): δc = 14.0, 22.9, 29.2, 29.8, 42.6, 94.6,
107.9, 110.7, 122.4, 124.6, 128.2, 129.9, 130.4, 130.9, 131.3, 133.0, 145.7, 159.6, 160.1, 165.4. HRMS (ESI) m/z calcd. for
C22H21ClN2O2[M+H]+ : 379.1207, found: 379.1207.
* Solvent peak at 7.26 is overlapped with this peaks, hence higher integration is obtained.
See 1H NMR spectra of both compounds at page S4 and S7 of ESI.
S4
Figure SS1: 3-(4-bromophenyl)-2-((2-morpholinoethyl)amino)furo[3,2-c]quinolin-4-ol (FQ1): 1H NMR
S5
Figure SS2: 3-(4-bromophenyl)-2-((2-morpholinoethyl)amino)furo[3,2-c]quinolin-4-ol (FQ1): 13C NMR
S6
Figure SS3: 3-(4-bromophenyl)-2-((2-morpholinoethyl)amino)furo[3,2-c]quinolin-4-ol (FQ1): HRMS
S7
Figure SS4: 3-(4-chlorophenyl)-2-(pentylamino)furo[3,2-c]quinolin-4-ol (FQ2): 1H NMR
S8
Figure SS5: 3-(4-chlorophenyl)-2-(pentylamino)furo[3,2-c]quinolin-4-ol (FQ2): 13C NMR
S9
Figure SS6: 3-(4-chlorophenyl)-2-(pentylamino)furo[3,2-c]quinolin-4-ol (FQ2): HRMS
S10
Figure SS7: UV-Vis Spectra of FQ1 (20μM in DMSO:MeOH = 1:9) in the presence of different ions (10 equiv.). The distinct behaviour
of Cu2+ (equimolar) is apparent from figure.
270 300 330 360 390 420 450
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
FQ
1A
l3+
gd3+
Ca2
+Fe3
+C
d2+
Cu2
+C
r3+
Co2
+K
+H
g2+
Li+
Mg2
+Pb2
+N
i2+
Na+
Mn2
+Z
n2+
Fe2
+
-0.10
-0.05
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
A0-A
FQ1 + Cu2+
FQ1 + Other metal
Abso
rban
ce (
a.u.)
Wavelength (nm)
S11
Figure SS8: UV-vis Spectra of FQ2 (20μM in DMSO:MeOH = 1: 9) in the presence of different ions (10 equiv.). The distinct behaviour
of Cu2+ (equimolar) is apparent from figure.
270 300 330 360 390 420 450
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
FQ
2A
l3+
Ca2
+C
o2+
Cu2
+
Li+
Cd2
+C
r3+
Fe2
+
K+
Fe3
+H
g2+
Pb2
+gd
3+M
g2+
Mn2
+N
a+N
i2+
Zn2
+-0.04
0.00
0.04
0.08
0.12
0.16
0.20
A0-A
FQ2 + Other metal
FQ2+Cu2+
Abso
rban
ce (
a.u.)
Wavelength (nm)
S12
Figure SS9: Fluorescence response of FQ1 (20μM in DMSO:MeOH = 1: 9) toward 10 equiv. of different metal ions after excitation at
370 nm.
400 450 500 550 600 650
0
3000
6000
9000
12000
15000
18000
21000
24000
FQ1, Ca2+
, Cd2+
, Co2+
, K+, Na
+, Li
+,
Hg2+
, Fe2+
, Nd3+
, Mg2+
, Mn2+
, Ni2+
,
Zn2+
, Pb2+
, Al3+
, Cr3+
, Gd3+
, Fe3+
.
Flu
ore
scen
ce I
nte
nsi
ty (
cps)
Wave length (nm)
Cu2+
S13
Figure SS10: Fluorescence response of FQ1 (20μM in DMSO:MeOH = 1: 9) toward 10 equiv. different metal ions after excitation at 370
nm wavelength.
400 450 500 550 600 650
0
3000
6000
9000
12000
15000
18000
21000
Cu2+
FQ2, Ca2+
, Cd2+
, Co2+
, K+, Na
+, Li
+,
Hg2+
, Fe2+
, Mg2+
, Mn2+
, Ni2+
, Pb2+
,
Zn2+
, Al3+
, Cr3+
, Gd3+
, Fe3+
, Nd3+
.
Flu
ore
scen
ce I
nte
nsi
ty (
cps)
Wavelength (nm)
S14
Figure SS11: Fluorescence responses of FQ1 (20μM in DMSO:MeOH = 1:9) in the presence of different metal ions.
S15
Figure SS12: Fluorescent titration of FQ1 (20 μM in DMSO:MeOH = 1:9) against Cu2+ (0.1 equiv. to 2.5 equiv.) after excitation at 370
nm wavelength.
400 440 480 520 560 600 640 680
0
3000
6000
9000
12000
15000
18000
21000
0 10 20 30 40 50
0
3000
6000
9000
12000
15000
18000
21000
Y = -865.1x + 18850
R² = 0.984
LOD = 1.52 x 10-7 M
Flu
ore
scen
ce I
nte
nsi
ty (
cps)
(Concentration of Cu2+
(M)
0 200000 400000 600000 800000 1000000 1200000
0.0000
0.0002
0.0004
0.0006
0.0008
0.0010
0.0012
0.0014
Y = 1.169E-09x + 2.478E-05
R² = 0.992
K = 2.11 x 104 M
-1
1/I
0-I
1/Cu2+
FQ1
Flu
ore
scen
t In
tensi
ty (
cps)
Wave length (nm)
0.0 equiv.
2.5 equiv.
S16
Figure SS13: Fluorescent titration of FQ2 (20 μM in DMSO:MeOH = 1:9) against Cu2+ (0.1 equiv. to 2.5 equiv.) after excitation at 370
nm wavelength.
400 450 500 550 600 650 700
0
3000
6000
9000
12000
15000
18000
21000
0 10 20 30 40 50
2000
4000
6000
8000
10000
12000
14000
16000
18000
20000
22000
Y = -766.1x + 19272
R² = 0.985
LOD = 2.13 x 10-7 M
Flu
ore
scen
ce I
nte
nsi
ty (
cps)
Concentration of Cu2+
(M)
0 200000 400000 600000 800000 1000000
0.0000
0.0002
0.0004
0.0006
0.0008
0.0010
0.0012
0.0014
0.0016
Y = 1.41E-09x - 2.65E-05
R² = 0.993
Ka = 1.87 x 104 M
-1
1/I
0-I
1/Cu2+
0.0 equiv.
FQ2F
luore
scen
ce I
nte
nsi
ty (
cps)
Wavelength (nm)
2.5 equiv.
S17
Figure SS14: Examination of selectivity of FQ1 (20 μM in DMSO:MeOH = 1:9) towards Cu2+ in the presence of interfering ions.
Al3
+Ca2
+Cd2
+Co2
+Cr3
+Fe
2+Fe
3+H
g2+
K+
Li+M
g2+
Mn2
+N
a+N
i2+
Pb2+
Zn2+
Nd3
+
0
3000
6000
9000
12000
15000
18000
21000
24000 FQ1+ various metal ions
FQ1+ Cu2+
+ various metal ions
Flu
ore
scen
ce I
nte
nsi
ty (
cps)
S18
Figure SS 15: Examination of selectivity of FQ2 (20 μM in DMSO:MeOH = 1:9) towards Cu2+ in the presence of interfering ions.
Al3
+C
a2+
Cd2
+C
r3+
Co2
+N
d3+
Fe2+
Fe3+
Mg2
+H
g2+
Mn2
+N
a+ K+
Ni2
+Zn2
+Pb
2+ Li+
0
3000
6000
9000
12000
15000
18000
21000
24000 FQ2 + various metal ions
FQ2 + Cu2+
+ various metal ions
Flu
ore
scen
ce I
nte
nsi
ty (
cps)
S19
Figure SS16: Change in fluorescence response with time at 465 and 460 nm respectively for compounds FQ1and FQ2.
0 10 20 30 40 50 60 70 80 90 100 110 120 130
0
5000
10000
15000
20000
25000
FQ1 + Cu2+
FQ2 + Cu2+
Flu
ore
scen
ce I
nte
nsi
ty (
cps)
Time (Min.)
S20
Figure SS17: Job’s plot to determine binding stoichiometry of compounds FQ1 with Cu2+
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1
0
2000
4000
6000
8000
10000
12000
14000
16000
18000
20000
22000
Flu
ore
scen
ce I
nte
nsi
ty (
cps)
FQ1/[FQ1+Cu2+
]
S21
Figure SS18: Job’s plot to determine binding stoichiometry of compounds FQ2 with Cu2+
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
0
2000
4000
6000
8000
10000
12000
14000
16000
18000
20000
Flu
ore
scen
ce I
nte
nsi
ty (
cps)
FQ2/[FQ2+Cu2+
]
S22
Figure SS19: HRMS of possible complex of compound FQ1 with Cu2+
S23
Figure SS20: HRMS of possible complex of compound FQ2 with Cu2+
S24
Figure SS21: Reversibility Studies
S25
Figure SS22: NMR Titration (FQ1) in the presence of different conc. of Cu2+ (DMSO-d6 was used as NMR solvent and TMS as
internal standard).
S26
Figure SS23: NMR Titration (FQ2) in the presence of different conc. of Cu2+ (DMSO-d6 was used as NMR solvent and TMS as
internal standard).
S27
Figure SS24: Effect of pH on Fluorescence quenching
2 3 4 5 6 7 8 9 10 11
0
3000
6000
9000
12000
15000
18000
21000
FQ1
FQ1 + Cu2+
FQ2
FQ2 + Cu2+
Flu
ore
scen
ce I
nte
nsi
ty (
cps)
pH
S28
Figure SS25: DFT study (Optimized structure of FQ1 and FQ2)
S1
Table SS1: Comparison of reported FQs with some of the recently developed sensors for
Cu2+
(flur = fluorescence, NM = Not Mentioned)
S.No. Sensor/probe Interaction Association
constant (Ka) M-1
LOD in M pH range
1 FQs (This work) Turn off
(flur)
Reversible
2.11 × 104
1.87 × 104
1.52 × 10-7
2.13 × 10-7
5.5-11
24h
Turn off (flur)
Irreversible
NM 0.5 × 10-7 5-7
34i
Conc.
dependent
Turn off (flur)
6.82 × 104 4.0 × 10-7 NM
48a P-Qs Turn on (flur)
irreversible
NM 1.5 × 10-6 7-9
64j
Turn on (flur) 1.1 × 1010 0.15 × 10-6 NM
74k
Turn off (flur) NM 1.27 × 10-4 NM
88b
Turn off (flur) 5.0 × 104 1.5 × 10-6 4-11
S2
Table SS2: Photophysical properties of FQ1 and FQ2
Comp. Emission Quantum
Yield
Detection
Limit (M)
Binding
Constant (M-1)
R2 I/I0 Response
Time (Min.)
ex/nm em/nm
FQ1 370 465 0.3915 1.52 x 10-7 2.11 x 104 0.984 0.027 2-3 min.
FQ1 +Cu2+ 370 459 0.0253
FQ2 370 460 0.3856 2.13 x 10-7 1.87 x 104 0.985 0.159 2-3 min.
FQ + Cu2+ 370 452 0.0597