Post on 13-Jun-2020
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Multiple Molecular Logic Functions and Molecular Calculation
Facilitated by Surfactant with its Versatility
Junhong Qian Xuhong Qian* Yufang Xu Shenyi Zhang
State Key Laboratory of Bioreactor Engineering and Shanghai Key Laboratory of
Chemical Biology, School of Pharmacy, East China University of Science and
Technology, Shanghai 200237, China
xhqian@ecust.edu.cn
Supporting Information
Materials. All the solvents and reagents were of analytic grade and used as received.
Water used was twice distilled. The pH values were adjusted with NaOH and HCl
aqueous solution. The pH was determined with a pH meter (Shanghai Rex Instrument
Factory, China; model PHS-3C), which was standardized with Aldrich buffers.
Absorption measurements were performed with a Varian Cary500 spectrophotometer
(1 cm quartz cell) and fluorescent spectra were recorded on a Varian Cary Eclipse
fluorescence spectrophotometer (1 cm quartz cell). Mass spectra (MS) were recorded
on an MA1212 instrument using standard conditions (ESI, 70 eV). All the
experiments were performed at 25.0 °C.
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Contents
Synthesis and characterization---------------------------------------------------------- P2
NMR spectra of compound 1 and 2---------------------------------------------------- P4
Two-input INH and XOR logic truth table ------------------------------------------ P5
Two-input INH, Pass 1 and XOR logic truth table----------------------------------P6
Two-input NOR, XOR and AND logic truth table----------------------------------P7
Two-input INH, PASS 1 and NOR logic truth table--------------------------------P8
Two-input YES, NO and OR logic truth table---------------------------------------P10
Two-input NO and OR logic truth table----------------------------------------------P11
Two-input PASS 0, NOR, NAND, INH and AND logic truth table-------------P12
Three-input NOR logic truth table ----------------------------------------------------P12
Three-input INIHIBIT logic truth table ----------------------------------------------P13
Synthesis The synthesis of compounds 1 and 2 from commercially available
compounds is illustrated in Scheme 1.
O OO
Br
N OO
NH2
Br
N ON
R
N(CH2CH2)2NCH3R=
ab
-H2O+
N NO
R
1 2
Scheme 1 preparation of compounds 1 and 2
Reagent: (a) NH2C2H4NH2, C2H5OH; (b) NH(CH2CH2)2NCH3, CH3OC2H4OH.
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N-(aminoethyl)-4-bromonaphthalene-1,8-dicarboximide (a): Ethylenediamine (2.0
g, 33.3 mmol) was added to a suspension of 4-bromonaphthalene-1,8-dicarboximide
(5.54 g, 20 mmol) in ethanol (50 mL). The mixture was then refluxed for 4 hours,
after which the solvent was evaporated under vacuum. The product crystallized from
ethanol. Yield 85%. M.p. 154.8 °C; MS: m/z (%) 318 (1%); 1H NMR (500 MHz,
CDCl3): δ8.65 (dd, 1H, 7-ArH), 8.56 (dd, 1H, 2-ArH), 8.41 (d, J = 7.9 Hz, 1H,
5-ArH), 8.02 (d, J = 7.8 Hz, 1H, 5-ArH), 7.82 (dd, 2H, 3,6-ArH), 4.27 (t, J = 6.6 Hz,
2H, -NCH2CH2NH2), 3.07 (t, J = 6.6 Hz, 2H, -NCH2CH2NH2).
1: To a solution of 5 mL of ethylene glycol monomethyl ether added 0.2 g (6.3 mmol)
of a and excess N-methyl piperidine (1 mL). The mixture was refluxed for 5 h under
N2 atmosphere and then the solvent was evaporated under vacuum. The product was
purified by chromatography using methanol /dichloromethane (1: 20, v/v) as eluant to
give 72 mg (36%) of 1 as yellow solid: 1H-NMR (400MHz, MD3OD), δ8.06 (d, J =
8.4 Hz, 1H), 7.99 (d, J = 7.6 Hz, 1H), 7.89 (d, J = 8.0 Hz, 1H), 7.43 (t, J = 8.0 Hz,
1H), 7.06 (d, J = 8.0 Hz, 1H), 4.04 (t, J = 8.6 Hz, 2H), 3.89 (t, J = 8.6 Hz, 2H), 3.17 (s,
4H), 2.78 (s, 4H), 2.46 (s, 3H), 13C NMR (100 MHz, CD3OD) δ = 160.2, 155.0, 154.5,
129.8, 129.1, 128.2, 126.4, 125.2, 120.0, 117.3, 114.4, 54.7, 52.8, 52.0, 44.7, 43.2
ppm. HR-MS (ES+) Calcd for ([M+H])+, 321.1715; Found, 321.1736. 2 was obtained
by the same procedure as orange solid 80 mg (40%): 1H-NMR (400MHz, MD3OD),
δ8.03 (d, J = 8.0 Hz, 1H), 7.83 (dd, J = 7.6 Hz, 2H), 7.39 (t, J = 7.6 Hz, 1H), 7.10 (t, J
= 8.0 Hz, 1H), 3.97 (t, J = 9.2 Hz, 2H), 3.79 (t, J = 8.8 Hz, 2H), 3.24 (s, 4H), 3.09 (s,
4H), 2.68 (s, 3H), 13C NMR (100 MHz, CD3OD) δ = 159.9, 154.2, 153.0, 129.5,
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128.8, 127.9, 127.2, 126.2, 125.4, 123.4, 115.0, 114.1, 54.2, 52.5, 51.1, 43.8, 43.1ppm.
HR-MS (ES+) Calcd for ([M+H])+, 321.1715; Found, 321.1714.
Figure 1 1H-NMR and 13C-NMR spectra of 1 (a, b) and 2 (c, d)
a b
c d
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450 500 550 600 650 7000
100
200
300
400
500
0
Input Output X Y INH:B XOR:D negative logic OH- H+ Abs426nm φ φ
0 0 0 (low, 0.054) 0 (low, 0.218) 0.218 0 1 1 (high, 0.162) 1 (high, 0.060) 0.060 1 0 0 (low, 0.100) 1 (high, 0.010) 0.010 1 1 0 (low, 0.055) 0 (low, 0.210) 0.201
I (a.
u.)
λ (nm)
a
1
300 360 420 480 540 6000.00
0.05
0.10
0.15
0.20
0.25
0
1
Input Output X Y OH- H+ Abs426nm Abs373nm
0 0 0.054 (low) 0.192 (high) 1 0 0.099 (low) 0.172 (high) 0 1 0.162 (high) 0.088 (low) 1 1 0.055 (low) 0.189 (high)
INHIBIT
Abs
λ (nm)
b
Figure 2 Fluorescence, UV-vis spectra and truth table of 1 in water in the presence of
chemical inputs (excited at 410 nm).
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300 360 420 480 540 6000.00
0.06
0.12
0.18
0.24
0.30
0
1
Input Output X Y INH PASS 1 OH- SDS Abs426nm Abs405nm
10-4M 8.4 mM 0 0 0.054 (low) 0.146 (high) 0 1 0.129 (high) 0.134 (high) 1 0 0.098 (low) 0.176 (high) 1 1 0.063 (low) 0.149 (high)
Abs
λ (nm)
a
450 500 550 600 650 7000
160
320
480
640
800
0
Input Output X Y INH:B XOR:D negative logic OH- SDS Abs426nm φ φ
10−4 8.2mΜ 0 0 0 (low, 0.053) 0 (low, 0.218) 0.218 0 1 1 (high, 0.129) 1 (high, 0.090) 0.090 1 0 0 (low, 0.098) 1 (high, 0.010) 0.010 1 1 0 (low, 0.063) 0 (low, 0.156) 0.156
I (a.
u.)
λ (nm)
b
1
Figure 3 Fluorescence, UV-vis spectra and truth table of 1 in the presence of chemical
inputs (excited at 410 nm).
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7
450 500 550 600 650 7000
100
200
300
400
500
input output SDS SDS φ 4.2 mM 4.2 mM
0 0 0.218 (high) 0 1 0.104 (low) 1 0 0.104 (low) 1 1 0.090 (low)
NOR I (a.
u.)
λ (nm)
a
300 350 400 450 500 550 6000.00
0.06
0.12
0.18
0.24
0.30 Input Output XSDS YSDS AND:C XOR:S 4.2mM 4.2mM Abs426nm Trans%405nm Abs405nm
0 0 0 (low, 0.054) 0 (low, 72) 0.135 0 1 0 (low, 0.041) 1 (high, 83) 0.082 1 0 0 (low, 0.041) 1 (high, 83) 0.082 1 1 1 (high, 0.131) 0 (low, 72) 0.134
01
Abs
l (nm)
b
Figure 4 Fluorecence, UV-vis spectra and truth table of 1 in water in the presence of
chemical inputs (excited at 410 nm).
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8
300 360 420 480 540 6000.00
0.05
0.10
0.15
0.20
0.25
0
1
Input Output X Y INH:B OH- H+ Abs425nm
0 0 0.0514 (low) 0 1 0.216 (high) 1 0 0.070 (low) 1 1 0.053 (low)
Abs
λ (nm)
a
300 360 420 480 540 6000.00
0.06
0.12
0.18
0.24
0.30
01
Input Output X Y INH PASS 1 OH- SDS Abs425nm Abs400nm
10-4M 8.4 mM 0 0 0.053 (low) 0.122 (high) 0 1 0.154 (high) 0.118 (high) 1 0 0.068 (low) 0.121 (high) 1 1 0.069 (low) 0.120 (high)
Abs
λ (nm)
b
Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2008
9
450 500 550 600 650 7000
100
200
300
400
500
600
input output SDS SDS φ 4.2 mM 4.2 mM
0 0 0.055 (high) 0 1 0.035 (low) 1 0 0.035 (low) 1 1 0.018 (low)
NOR
I (a.
u.)
λ (nm)
c
Figure 5 UV-vis, fluorescence spectra and truth table of 2 in water in the presence of
chemical inputs (excited at 395 nm).
Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2008
10
300 360 420 480 540 6000.00
0.06
0.12
0.18
0.24
0.30
Input Output X Y H+ SDS Abs425nm Abs390nm
10-4M 4.2 mM 0 0 0.053 (low) 0.122 (high) 0 1 0.047 (low) 0.059 (low) 1 0 0.217 (high) 0.121 (high) 1 1 0.175 (high) 0.086 (low)
YES(X) NO (Y) Abs
λ (nm)
1
0
a
300 360 420 480 540 6000.00
0.05
0.10
0.15
0.20
0.25
Abs
λ (nm)
input output
H+
SDS(8.4 mM) A425 0 0 0.056 (low) 1 0 0.217 (high) 0 1 0.155 (high) 1 1 0.189 (high)
OR1
0
b
Figure 6 UV-vis spectra and truth table of 2 in water in the presence of chemical
inputs.
Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2008
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300 360 420 480 540 6000.00
0.05
0.10
0.15
0.20
0.25
input output
H+
SDS(4.2 mM) A425 0 0 0.046 0 1 0.155 1 0 0.175 1 1 0.189
ORAbs
λ (nm)
1
0
a
450 500 550 600 650 700
0
30
60
90
120
150
0
input output
H+
SDS(4.2 mM) φ 0 0 0.035 (high) 0 1 0.018 (high) 1 0 0.005 (low) 1 1 0.003 (low)
NO
I (a.
u.)
λ (nm)
b
1
Figure 7 Fluorescence, UV-vis spectra and truth table of 2 in 4.2 mM SDS aqueous
solution in the presence of chemical inputs (excited at 395 nm).
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Table 1 Two-input logic truth table of 2
Input 1 SDS (4.2 mM)
Input 2 OH− (pH 9.5)
Output 1 A 400
Output 2 A 426
Output 3 Φ
0 0 1 (0.117) 0 (0.051) 1 (0.055) 0 1 1 (0.123) 0 (0.071) 0 (0.016) 1 0 0 (0.059) 0 (0.047) 0 (0.035) 1 1 1 (0.118) 0 (0.069) 0 (0.020) Pass 0 NOR
Table 2 Two-input logic truth table of 2 in 4.2 mM SDS aqueous solution
Input 1 SDS (4.2 mM)
Input 2 OH− (pH 9.5)
Output 1 A 400
Output 2 A 426
Output 3 Φ
0 0 0 (0.059) 0 (0.047) 0 (0.035) 0 1 1 (0.118) 0 (0.069) 0 (0.020) 1 0 1 (0.120) 1 (0.155) 0 (0.018) 1 1 1 (0.122) 0 (0.072) 1 (0.057) NAND INH AND
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Table 3 Three-input NOR logic truth table of 1
Input 1 SDS (4.2 mM)
Input 2 SDS (4.2 mM)
Input 3 H+ (pH 3.5)
Output 1 A 373
Output 2 A 426
Output 3 Φ
0 0 0 1 (0.192) 0 (0.054) 1 (0.218) 0 0 1 0 (0.084) 1 (0.163) 0 (0.060) 0 1 0 0 (0.084) 0 (0.043) 0 (0.104) 0 1 1 0 (0.040) 1 (0.113) 0 (0.011) 1 0 0 0 (0.084) 0 (0.043) 0 (0.104) 1 0 1 0 (0.040) 1 (0.114) 0 (0.011) 1 1 0 0 (0.090) 1 (0.127) 0 (0.090) 1 1 1 0 (0.083) 1 (0.130) 0 (0.080) NOR
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Table 4 Three-input INHIBIT logic truth table 0f 1
Input 1 SDS (4.2 mM)
Input 2 SDS (4.2 mM)
Input 3 OH− (pH 9.5)
Output 1 A 373
Output 2 A 426
Output 3 Φ
0 0 0 1 (0.192) 0 (0.054) 1 (0.218) 0 0 1 1 (0.188) 0 (0.056) 0 (0.010) 0 1 0 0 (0.084) 0 (0.043) 0 (0.104) 0 1 1 1 (0.174) 0 (0.098) 0 (0.010) 1 0 0 0 (0.084) 0 (0.043) 0 (1049) 1 0 1 1 (0.174) 0 (0.098) 0 (0.010) 1 1 0 0 (0.090) 1 (0.127) 0 (0.090) 1 1 1 1 (0.152) 0 (0.096) 1 (0.156) INH
Acknowledgement: This work was supported by the National Natural Science
Foundation of China (20536010) and the National Key Project for Basic Research
(2003CB 114400).
Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2008