A Novel Detection Technique of Hydrazine Hydrate: Modality … · A Novel Detection Technique of...

A Novel Detection Technique of Hydrazine Hydrate: Modality Change of Hydrogen-Bonding Induced Rapid and Ultrasensitive Colorimetric Assay

Zhenlu Zhao,a Kelong Ai,b Guo Zhang,b Ying Gao,a Xiuyun Yang,* a and Yunhui Li* a

Supporting information

aSchool of Chemical & Enviromental Engineering, Changchun University of Science and Technology, Changchun,

130022, P. R. China.

bState Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese

Academy of Science, Changchun, 130022, P. R. China.

E-mail: [email protected]; [email protected]

Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011

Experimental Section

Chemicals:

Hydrogen tetrachloroaurate (III) trihydrate was purchased from Alfa Aesar. 2,6-pyridinedicarboxylic acid (PDCA)

was obtained from Aldrich. Sodium citrate tribasic dihydrate was purchased from Sigma. All aqueous solutions

were prepared with ultrapure water from a Milli-Q Plus system (Millipore). Hydrazine hydrate was obtained

commercially from the Beijing Chemical Reagent Plant (Beijing, China). All other chemicals are of analytical

grade and used without further purification unless noted.

Preparation of Au nanoparticles

Au nanoparticles (Au NPs) were synthesized by the reduction of HAuCl4 by sodium citrate. Briefly, 50 ml of 1

mM HAuCl4 was heated to reflux with stirring, and then 5 ml of 38.8 mM sodium citrate was rapidly added. The

solution was kept continually boiling for another 30 min to give a wine red solution. The final concentration of Au

NPs was determined to be 10 nM, and the average diameter is 12 nm.

Design of Au nanoparticles-based colorimetric sensing system (ANCSS) and detection of hydrazine hydrate

Firstly, 0.1 M PDCA was prepared by dissolving PDCA in 0.2 M NaOH aqueous solution. Then, 0.1 M PDCA

was adding to as-prepared Au NPs solution with different volume ratios (VAu/VPDCA = 300:x) under stirring.

Finally, the ANCSS was obtained by adjusting pH value of the mixture to 7 using 0.2 M NaOH solution.

Aliquots of the Au NPs solution (300 μl) was added with various concentration solutions of hydrazine hydrate (6

μl), which were obtained by using serial dilution of the stock solution (0.1 M). After the addition of hydrazine

hydrate with different concentration, the response of the ANCSS stimulated by hydrazine hydrate was monitored

by UV-vis spectroscopy within 30 seconds at room temperature.

Characterization:

Transmission electron microscopy (TEM) images were obtained on a JEOL 2010 transmission electron

microscopy operated at an accelerating voltage of 200 kV. UV–vis spectra were recorded on a Cary 50

UV–vis–NIR spectrophotometer (Varian, U.S.A.) Photographs for color changes were taken with a PENTAX

*ISTD digital camera.


Fingure S1. TEM images of Au NPs (a) and as–modified Au NPs (b) at pH=7.0.

a b


Fingure S2. UV-vis absorption spectra of the Au NPs, as–modified Au NPs, and as–modified Au NPs after one

week. Inset: the corresponding visual colour of three samples (from left to right: Au NPs, as-modified Au NPs,

as-modified Au NPs after one week).

400 450 500 550 600 650 700 750 800-0.1

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

Au NPs as-modified Au NPs as-modified Au NPs one week later

Ab

so

rba

nce

Wavelength / nm


Fingure S3. (a) The response of the ANCSS stimulated by hydrazine hydrate (10 μΜ) at various pH values. (b)

The response of the ANCSS with different ratios of Au and PDCA (VAu/VPDCA) stimulated by hydrazine hydrate

(10 μΜ).

0 10 20 30 40 50 600.00

0.03

0.06

0.09

0.12

0.15

0.18

A 0 51

9 -

A 5

19

Au NPs : PDCA = 300 : X ( V Au NPs

/ V PDCA

)

b

5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5

0.05

0.06

0.07

0.08

0.09

0.10

0.11

A 0 51

9 -

A 5

19

PH

a


Fingure S4. Selectivity of the ANCSS for hydrazine hydrate over other common metallic cations under the

optimized conditions: the concentration of each of the cations and hydrazine hydrate was 10 μM. (a) UV-vis

absorption spectra of the ANCSS upon addition of hydrazine hydrate and common metallic cations under identical

conditions. (b) The corresponding plot of (A0519-A519)/A

0519 intensity of the optimized ANCSS in the presence of

hydrazine hydrate and common metallic cations.

0.00

0.02

0.04

0.06

0.08

0.10

( A

0 519 -

A 5

19 )

/ A 0 5

19

Ni2+ Na+ Co2+Mn2+ Fe3+

Fe2+ Li+ Mg2+ K+Hg2+ Cu2+ Ba2+

Ca2+ Al3+Cd2+ Pb2+ Ag+ N2H4

400 450 500 550 600 650 700 750 800-0.1

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9A

bs

orb

ance

Wavelength / nm



Ca2+ Al3+Cd2+ Pb2+ Ag+

N2H4

0


Fingure S5. Selectivity of the ANCSS for hydrazine hydrate over other common anions under the optimized

conditions: the concentration of each of the ations and hydrazine hydrate was 10 μM. (a) UV-vis absorption

spectra of the ANCSS upon addition of hydrazine hydrate and common anions under identical conditions. (b) The

corresponding plot of (A0519-A519)/A

0519 intensity of the optimized ANCSS in the presence of hydrazine hydrate

and common ations.

0.00

0.02

0.04

0.06

0.08

0.10

( A

0 519 -

A 5

19 )

/ A 0 5

19

C6H5O73-

C2O42-

EDTA2-

Ac-

SO42-

ClO4-

NO2-

CO32-

SO32-

Br-

Cl-

F-

NO3-

HPO42-

N3-

S2O82-

N2H4

400 450 500 550 600 650 700 750 800-0.1

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

Ab

so

rban

ce

Wavelength / nm

C6H5O73-

C2O42-

EDTA2- Ac- SO42-ClO4

-NO2

-CO3

2- SO32- Br- Cl- F-

NO3- HPO4

2- N3- S2O8

2-

N2H4

0


Fingure S6. Selectivity of the ANCSS for hydrazine hydrate over other common neutral interfering species under

the optimized conditions: the concentration of each of the common neutral interfering species and hydrazine

hydrate was 10 μM. (a) UV-vis absorption spectra of the ANCSS upon addition of hydrazine hydrate and common

neutral interfering species under identical conditions. (b) The corresponding plot of (A0519-A519)/A

0519 intensity of

the optimized ANCSS in the presence of hydrazine hydrate and common neutral interfering species.

0.00

0.02

0.04

0.06

0.08

0.10

( A

0 519 -

A 5

19 )

/ A 0 5

19

CH3NH2

C6H12O6

(NH2)2CO

N (CH2CH2OH) 3

C6H8O6

CH3OH

HCHO

NH3.H2O

NaBH4

NH2OH.HCl

GHS N2H4

400 450 500 550 600 650 700 750 800-0.1

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

Ab

so

rban

ce

Wavelength / nm

CH3NH2 C6H12O6 (NH2)2CO N(CH2CH2OH)3 C6H8O6 CH3OH HCHO NH3.H2O NaBH4 NH2OH.HClGHS

N2H4

0


Fingure S7. Selectivity of the ANCSS for hydrazine hydrate over other common molecules with similar structures

under the optimized conditions: the concentration of each of the common molecules with similar structures and

hydrazine hydrate was 10 μM. UV-vis absorption spectra of the ANCSS upon addition of hydrazine hydrate (a),

methylenediamine dihydrochloride (b), 1,2-ethanediamine (c) and 1,4-benzenediamine (d) under identical

conditions. The results show that Au NPs undergo inter-particle cross-linking to form aggregates stimulated by

those molecules with similar structures. However, when compared with the UV-vis absorption spectra of Au NPs

stimulated by hydrazine hydrate, the peak profile is quite different and another obvious absorption band is

observed upon exposure of ANCSS to those molecules with similar structures, revealing that such ANCSS

provides a remarkable selectivity.

400 450 500 550 600 650 700 750 800-0.1

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7(a)

Ab

so

rba

nce

Wavelength / nm

Blank Hydrazine Hydrate

400 450 500 550 600 650 700 750 800-0.1

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7(c)

Ab

so

rba

nce

Wavelength / nm

Blank 1,2-ethanediamine

400 450 500 550 600 650 700 750 800-0.1

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

Blank 1,4-benzenediamine

Ab

sorb

anc

e

Wavelength / nm

(d)

Blank Methylenediamine dihydrochloride

400 450 500 550 600 650 700 750 800-0.1

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7(b)

Ab

sorb

anc

e

Wavelength / nm


Fingure S8. Specificity of the ANCSS for hydrazine hydrate over other analytes under the optimized conditions:

the concentration of each of the analytes and hydrazine hydrate was 10 μM and 100 μΜ, respectively. UV-vis

absorption spectra of the ANCSS upon addition of hydrazine hydrate and common metallic cations (a), anions (b),

and neutral interfering species (c) under identical conditions.

400 450 500 550 600 650 700 750 800-0.1

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

Ab

sorb

ance

Wavelength / nm



Ca2+ Al3+Cd2+ Pb2+ Ag+

N2H4

0(a)

400 450 500 550 600 650 700 750 800-0.1

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

Ab

so

rba

nce

Wavelength / nm

C6H5O73-

C2O42-

EDTA2- Ac- SO42-ClO4

-NO2

-CO3

2- SO32- Br- Cl- F-

NO3- HPO4

2-N3

- S2O82-

N2H4

0(b)

400 450 500 550 600 650 700 750 800-0.1

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

Ab

sorb

ance

Wavelength / nm

CH3NH2 C6H12O6 (NH2)2CO N(CH2CH2OH)3 C6H8O6 CH3OH HCHO NH3.H2O NaBH4 NH2OH.HClGHS

N2H4

0(c)


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