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 a School of Chemical & Enviromental Engineering, Changchun University of Science and Technology, Changchun, 1322, P. R. China. b State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Science, Changchun, 1322, P. R. China. E-mail: liyh@cust.edu.cn; yangxiuyun@cust.edu.cn
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 HAuCl 4 by sodium citrate. Briefly, 5 ml of 1 mm HAuCl 4 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 3 min to give a wine red solution. The final concentration of Au NPs was determined to be 1 nm, and the average diameter is 12 nm. Design of Au nanoparticles-based colorimetric sensing system (ANCSS) and detection of hydrazine hydrate Firstly, M PDCA was prepared by dissolving PDCA in M NaOH aqueous solution. Then, M PDCA was adding to as-prepared Au NPs solution with different volume ratios (V Au /V PDCA = 3:x) under stirring. Finally, the ANCSS was obtained by adjusting ph value of the mixture to 7 using M NaOH solution. Aliquots of the Au NPs solution (3 μl) was added with various concentration solutions of hydrazine hydrate (6 μl), which were obtained by using serial dilution of the stock solution ( 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 3 seconds at room temperature. Characterization: Transmission electron microscopy (TEM) images were obtained on a JEOL 21 transmission electron microscopy operated at an accelerating voltage of 2 kv. UV vis spectra were recorded on a Cary 5 UV vis NIR spectrophotometer (Varian, U.S.A.) Photographs for color changes were taken with a PENTAX *ISTD digital camera.
a b Fingure S1. TEM images of Au NPs (a) and as modified Au NPs (b) at ph=7..
Electronic Supplementary Material (ESI) for Chemical Communications Au NPs as-modified Au NPs as-modified Au NPs one week later 4 45 5 55 6 65 7 75 8 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).
1 a 8 b 5 9 2 A 519 - A 519 8 7 A 519 - A 519 9 6 6 3 5 5.5 6. 6.5 7. 7.5 8. 8.5 9. 9.5 PH 1 2 3 4 5 6 Au NPs : PDCA = 3 : X ( V Au NPs / V PDCA ) Fingure S3. (a) The response of the ANCSS stimulated by hydrazine hydrate (1 μμ) at various ph values. (b) The response of the ANCSS with different ratios of Au and PDCA (V Au /V PDCA ) stimulated by hydrazine hydrate (1 μμ).
.9 Ni 2+ Na + Co 2+ Mn 2+ Fe 3+ Fe 2+ Li + Mg 2+ K + Hg 2+ Cu 2+ Ba 2+ Ca 2+ Al 3+ Cd 2+ Pb 2+ Ag + N 2 8 ( A 519 - A 519 ) / A 519 6 4 2 Ni 2+ Na + Co 2+ Mn 2+ Fe 3+ Fe 2+ Li + Mg 2+ K + Hg 2+ Cu 2+ Ba 2+ Ca 2+ Al 3+ Cd 2+ Pb 2+ Ag + N 2 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 1 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 (A 519-A 519 )/A 519 intensity of the optimized ANCSS in the presence of hydrazine hydrate and common metallic cations.
.9 3- C 6 H 5 O 7 C2 O - - 4 EDTA Ac SO4 ClO4 - NO - - - 2 CO3 SO3 Br Cl F - - NO3 HPO4 N3 S2 O 8 N 2 8 ( A 519 - A 519 ) / A 519 6 4 2 C 2 O 4 Ac - CO 3 - Br - ClO 4 3- C 6 H 5 O 7 EDTA - SO 4 NO 2 SO 3 Cl - F - NO 3 - - N 3 HPO 4 S 2 O 8 N2 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 1 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 (A 519-A 519 )/A 519 intensity of the optimized ANCSS in the presence of hydrazine hydrate and common ations.
.9 CH 3 NH 2 C 6 H 12 O 6 (NH 2 ) 2 CO N(CH 2 CH 2 OH) 3 C 6 H 8 O 6 CH 3 OH HCHO NH 3.H 2 O NaB GHS NH 2 OH.HCl N 2 8 ( A 519 - A 519 ) / A 519 6 4 2 C 6 H 12 O 6 NH 2 OH.HCl NH N (CH 2 CH 2 OH) 3.H 2 O 3 CH 3 OH CH 3 NH 2 (NH 2 ) 2 CO C 6 H 8 O 6 HCHO NaB GHS N 2 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 1 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 (A 519-A 519 )/A 519 intensity of the optimized ANCSS in the presence of hydrazine hydrate and common neutral interfering species.
(a) (b) Blank Hydrazine Hydrate Blank Methylenediamine dihydrochloride (c) (d) Blank 1,ethanediamine Blank 1,4-benzenediamine 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 1 μm. UV-vis absorption spectra of the ANCSS upon addition of hydrazine hydrate (a), methylenediamine dihydrochloride (b), 1,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.
(a) Ni 2+ Na + Co 2+ Mn 2+ Fe 3+ Fe 2+ Li + Mg 2+ K + Hg 2+ Cu 2+ Ba 2+ Ca 2+ Al 3+ Cd 2+ Pb 2+ Ag + N 2 (b) 3- C 6 H 5 O 7 C2 O - - - 4 EDTA Ac SO4 ClO4 NO - - - 2 CO3 SO3 Br Cl F - - NO3 HPO4 N3 S2 O 8 N 2 (c) CH 3 NH 2 C 6 H 12 O 6 (NH 2 ) 2 CO N(CH 2 CH 2 OH) C 3 6 H 8 O 6 CH 3 OH HCHO NH 3.H 2 O NaB GHS NH 2 OH.HCl N 2 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 1 μm and 1 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.