Multiple Molecular Logic Functions and Molecular ... · Multiple Molecular Logic Functions and...

1

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

[email protected]

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.

Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2008

2

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.


3

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,


4

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


5

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).


6

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).


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



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


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



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.


11

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).


12

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



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


13

Table 3 Three-input NOR logic truth table of 1



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


14

Table 4 Three-input INHIBIT logic truth table 0f 1




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).


Multiple Molecular Logic Functions and Molecular ... · Multiple Molecular Logic Functions and...

Documents

Transcript of Multiple Molecular Logic Functions and Molecular ... · Multiple Molecular Logic Functions and...