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Nano Research 2017, 10(6): 1932-1941 https://doi.org/10.1007/s12274-016-1378-1
Research Article | Issue | Published: 21 February 2017

Modulating the growth of cysteine-capped cadmium sulfide quantum dots with enzymatically produced hydrogen peroxide

Show Author's Information Ruta Grinyte,  Javier Barroso,  Laura Saa,  Valeri Pavlov( )
Biosensing Unit CIC BiomaGUNE, Parque Tecnológico de San Sebastian, Paseo Miramón 182, Donostia-San Sebastián 20014 Spain
Keywords:
quantum dots, fluorescence, hydrogen peroxide, photoelectrochemistry, enzyme
Cite this article:
Grinyte R, Barroso J, Saa L, et al. Modulating the growth of cysteine-capped cadmium sulfide quantum dots with enzymatically produced hydrogen peroxide. Nano Research, 2017, 10(6): 1932-1941. https://doi.org/10.1007/s12274-016-1378-1
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Abstract Full text Electronic supplementary material About this article

Cysteine (CSH) readily stabilizes cadmium sulfide quantum dots (CdS QDs) that grow in aqueous buffered solutions. The oxidation of CSH by hydrogen peroxide (H2O2) at room temperature yields cystine (CSSC), which is less efficient in stabilizing CdS QDs compared to CSH. Herein, we demonstrate that such oxidation causes a decrease in the formation rate of CSH-capped CdS QDs from Cd2+ and S2- ions. For the first time, we combined the oxidation of CSH with the glucose oxidase (GOx)-assisted biocatalytic oxidation of D-glucose, which leads to a buildup of H2O2 in the reaction mixture. The enzymatically modulated in situ growth of CdS QDs was monitored using two techniques: fluorescence spectroscopy and photoelectrochemical (PEC) analysis. This system enables quantification of GOx and glucose in human serum.


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Electronic supplementary material
About this article

Modulating the growth of cysteine-capped cadmium sulfide quantum dots with enzymatically produced hydrogen peroxide

Show Author's information Ruta Grinyte, Javier Barroso, Laura Saa, Valeri Pavlov( )
Biosensing Unit CIC BiomaGUNE, Parque Tecnológico de San Sebastian, Paseo Miramón 182, Donostia-San Sebastián 20014 Spain

Abstract

Cysteine (CSH) readily stabilizes cadmium sulfide quantum dots (CdS QDs) that grow in aqueous buffered solutions. The oxidation of CSH by hydrogen peroxide (H2O2) at room temperature yields cystine (CSSC), which is less efficient in stabilizing CdS QDs compared to CSH. Herein, we demonstrate that such oxidation causes a decrease in the formation rate of CSH-capped CdS QDs from Cd2+ and S2- ions. For the first time, we combined the oxidation of CSH with the glucose oxidase (GOx)-assisted biocatalytic oxidation of D-glucose, which leads to a buildup of H2O2 in the reaction mixture. The enzymatically modulated in situ growth of CdS QDs was monitored using two techniques: fluorescence spectroscopy and photoelectrochemical (PEC) analysis. This system enables quantification of GOx and glucose in human serum.

Keywords: quantum dots, fluorescence, hydrogen peroxide, photoelectrochemistry, enzyme

References(45)

1

Katz, E.; Willner, I. Integrated nanoparticle-biomolecule hybrid systems: Synthesis, properties, and applications. Angew. Chem., Int. Ed. 2004, 43, 6042-6108.
DOI Google Scholar
2

Liz-Marzán, L. M. Nanometals: Formation and color. Mater. Today 2004, 7, 26-31.
DOI Google Scholar
3

Li, H.; Xu, D. K. Silver nanoparticles as labels for applications in bioassays. TrAC-Trends Anal. Chem. 2014, 61, 67-73.
DOI Google Scholar
4

Omidfar, K.; Khorsand, F.; Darziani Azizi, M. New analytical applications of gold nanoparticles as label in antibody based sensors. Biosens. Bioelectron. 2013, 43, 336-347.
DOI Google Scholar
5

Mehrabi, M.; Wilson, R. Intercalating gold nanoparticles as universal labels for DNA detection. Small 2007, 3, 1491-1495.
DOI Google Scholar
6

David, C.; Guillot, N.; Shen, H.; Toury, T.; de la Chapelle, M. L. SERS detection of biomolecules using lithographed nanoparticles towards a reproducible SERS biosensor. Nanotechnology 2010, 21, 475501.
DOI Google Scholar
7

Jia, K.; Adam, P. M.; Marks, R. S.; Ionescu, R. E. Fixed Escherichia coli bacterial templates enable the production of sensitive SERS-based gold nanostructures. Sens. Actuat. B-Chem. 2015, 211, 213-219.
DOI Google Scholar
8

Marks, R. S.; Abdulhalim, I. Nanomaterials for Water Management: Signal Amplification for Biosensing from Nanostructures; Pan Stanford: Boca Ratón, 2016.
9

Jia, K.; Bijeon,J.-L.; Adam,P.-M.; Ionescu, R. E. Large scale fabrication of gold nano-structured substrates via high temperature annealing and their direct use for the LSPR detection of atrazine. Plasmonics 2013, 8, 143-151.
DOI Google Scholar
10

Mayilo, S.; Kloster, M. A.; Wunderlich, M.; Lutich, A.; Klar, T. A.; Nichtl, A.; Kürzinger, K.; Stefani, F. D.; Feldmann, J. Long-range fluorescence quenching by gold nanoparticles in a sandwich immunoassay for cardiac troponin T. Nano Lett. 2009, 9, 4558-4563.
DOI Google Scholar
11

Saidi, A.; Mirzaei, M.; Zeinali, S. Using antibody coated gold nanoparticles as fluorescence quenchers for simultaneous determination of aflatoxins (B1, B2) by soft modeling method. Chemom. Intell. Lab. Syst. 2013, 127, 29-34.
DOI Google Scholar
12

Mirkin, C. A.; Letsinger, R. L.; Mucic, R. C.; Storhoff, J. J. A DNA-based method for rationally assembling nanoparticles into macroscopic materials. Nature 1996, 382, 607-609.
DOI Google Scholar
13

Pavlov, V.; Xiao, Y.; Shlyahovsky, B.; Willner, I. Aptamer-functionalized Au nanoparticles for the amplified optical detection of thrombin. J. Am. Chem. Soc. 2004, 126, 11768- 11769.
DOI Google Scholar
14

Xiao, Y.; Pavlov, V.; Shlyahovsky, B.; Willner, I. An OsⅡ-bisbipyridine-4-picolinic acid complex mediates the biocatalytic growth of Au nanoparticles: Optical detection of glucose and acetylcholine esterase inhibition. Chem. —Eur. J. 2005, 11, 2698-2704.
DOI Google Scholar
15

Fanjul-Bolado, P.; Hernández-Santos, D.; González-García, M. B.; Costa-García, A. Alkaline phosphatase-catalyzed silver deposition for electrochemical detection. Anal. Chem. 2007, 79, 5272-5277.
DOI Google Scholar
16

Shlyahovsky, B.; Katz, E.; Xiao, Y.; Pavlov, V.; Willner, I. Optical and electrochemical detection of NADH and of NAD+-dependent biocatalyzed processes by the catalytic deposition of copper on gold nanoparticles. Small 2005, 1, 213-216.
DOI Google Scholar
17

Pavlov, V. Enzymatic growth of metal and semiconductor nanoparticles in bioanalysis. Part. Part. Syst. Charact. 2014, 31, 36-45.
DOI Google Scholar
18

Merkoçi, A. Biosensing Using Nanomaterials; John Wiley & Sons, Inc. : Hoboken, New Jersey, 2009.
19

Garai-Ibabe, G.; Saa, L.; Pavlov, V. Enzymatic product-mediated stabilization of CdS quantum dots produced in situ: Application for detection of reduced glutathione, NADPH, and glutathione reductase activity. Anal. Chem. 2013, 85, 5542-5546.
DOI Google Scholar
20

Saa, L.; Mato, J. M.; Pavlov, V. Assays for methionine γ-lyase and S-adenosyl-L-homocysteine hydrolase based on enzymatic formation of CdS quantum dots in situ. Anal. Chem. 2012, 84, 8961-8965.
DOI Google Scholar
21

Chatterjee, A.; Priyam, A.; Das, S. K.; Saha, A. Size tunable synthesis of cysteine-capped CdS nanoparticles by γ-irradiation. J. Colloid Interface Sci. 2006, 294, 334-342.
DOI Google Scholar
22

Kumar, P.; Kumar, P.; Bharadwaj, L. M.; Paul, A. K.; Sharma, S. C.; Kush, P.; Deep, A. Aqueous synthesis of L-cysteine stabilized water-dispersible CdS: Mn quantum dots for biosensing applications. BioNanoScience 2013, 3, 95-101.
DOI Google Scholar
23

Luo, D. Y.; Smith, S. W.; Anderson, B. D. Kinetics and mechanism of the reaction of cysteine and hydrogen peroxide in aqueous solution. J. Pharm. Sci. 2005, 94, 304-316.
DOI Google Scholar
24

Winterbourn, C. C.; Metodiewa, D. Reactivity of biologically important thiol compounds with superoxide and hydrogen peroxide. Free Radical Biol. Med. 1999, 27, 322-328.
DOI Google Scholar
25

Barton, J. P.; Packer, J. E.; Sims, R. J. Kinetics of the reaction of hydrogen peroxide with cysteine and cysteamine. J. Chem. Soc., Perkin Trans. 1973, 1547-1549.
DOI Google Scholar
26

Bankar, S. B.; Bule, M. V.; Singhal, R. S.; Ananthanarayan, L. Glucose oxidase—An overview. Biotechnol. Adv. 2009, 27, 489-501.
DOI Google Scholar
27

Zhao,W.-W.; Xu,J.-J.; Chen,H.-Y. Photoelectrochemical bioanalysis: The state of the art. Chem. Soc. Rev. 2015, 44, 729-741.
DOI Google Scholar
28

Devadoss, A.; Sudhagar, P.; Terashima, C.; Nakata, K.; Fujishima, A. Photoelectrochemical biosensors: New insights into promising photoelectrodes and signal amplification strategies. J. Photochem. Photobiol. C 2015, 24, 43-63.
DOI Google Scholar
29

Yue, Z.; Lisdat, F.; Parak, W. J.; Hickey, S. G.; Tu, L. P.; Sabir, N.; Dorfs, D.; Bigall, N. C. Quantum-dot-based photoelectrochemical sensors for chemical and biological detection. ACS Appl. Mater. Interfaces 2013, 5, 2800-2814.
DOI Google Scholar
30

Zhou, H.; Liu, J.; Zhang, S. S. Quantum dot-based photoelectric conversion for biosensing applications. TrAC-Trends Anal. Chem. 2015, 67, 56-73.
DOI Google Scholar
31

Zhao,W.-W.; Wang, J.; Zhu,Y.-C.; Xu,J.-J.; Chen,H.-Y. Quantum dots: Electrochemiluminescent and photoelectrochemical bioanalysis. Anal. Chem. 2015, 87, 9520-9531.
DOI Google Scholar
32

Walcarius, A. Electrocatalysis, sensors and biosensors in analytical chemistry based on ordered mesoporous and macroporous carbon-modified electrodes. TrAC-Trends Anal. Chem. 2012, 38, 79-97.
DOI Google Scholar
33

Long,Y.-T.; Kong, C.; Li,D.-W.; Li, Y.; Chowdhury, S.; Tian, H. Ultrasensitive determination of cysteine based on the photocurrent of nafion-functionalized CdS-MV quantum dots on an ITO electrode. Small 2011, 7, 1624-1628.
DOI Google Scholar
34

Zhao,W.-W.; Ma,Z.-Y.; Yan,D.-Y.; Xu,J.-J.; Chen,H.-Y. In situ enzymatic ascorbic acid production as electron donor for CdS quantum dots equipped TiO2 nanotubes: A general and efficient approach for new photoelectrochemical immunoassay. Anal. Chem. 2012, 84, 10518-10521.
DOI Google Scholar
35

Gao, Y.; Ding, X.; Liu, J.; Wang, L.; Lu, Z.; Li, L.; Sun, L. Visible light driven water splitting in a molecular device with unprecedentedly high photocurrent density. J. Am. Chem. Soc. 2013, 135, 4219-4222.
DOI Google Scholar
36

Iyer, R.; Pavlov, V.; Katakis, I.; Bachas, L. G. Amperometric sensing at high temperature with a "Wired" thermostable glucose-6-phosphate dehydrogenase from Aquifex aeolicus. Anal. Chem. 2003, 75, 3898-3901.
DOI Google Scholar
37

Vreeke, M. S.; Yong, K. T.; Heller, A. A thermostable hydrogen peroxide sensor based on "Wiring" of soybean peroxidase. Anal. Chem. 1995, 67, 4247-4249.
DOI Google Scholar
38

McNaught, A. D.; Wilkinson, A. IUPAC compendium of chemical terminology. In Gold Book; Blackwell Science: Oxford, UK, 1997.
39

Saa, L.; Pavlov, V. Enzymatic growth of quantum dots: Applications to probe glucose oxidase and horseradish peroxidase and sense glucose. Small 2012, 8, 3449-3455.
DOI Google Scholar
40

Grinyte, R.; Garai-Ibabe, G.; Saa, L.; Pavlov, V. Application of photocatalytic cadmium sulfide nanoparticles to detection of enzymatic activities of glucose oxidase and glutathione reductase using oxidation of 3, 3', 5, 5'-tetramethylbenzidine. Anal. Chim. Acta 2015, 881, 131-138.
DOI Google Scholar
41

Rodriguez, B. L.; Abbott, R. D.; Fujimoto, W.; Waitzfelder, B.; Chen, R.; Masaki, K.; Schatz, I.; Petrovitch, H.; Ross, W.; Yano, K. et al. The American Diabetes Association and World Health Organization classifications for diabetes: Their impact on diabetes prevalence and total and cardiovascular disease mortality in elderly Japanese-American men. Diabetes Care 2002, 25, 951-955.
DOI Google Scholar
42

Li, W. B.; Qian, D. P.; Wang, Q. H.; Li, Y. B.; Bao, N.; Gu, H. Y.; Yu, C. M. Fully-drawn origami paper analytical device for electrochemical detection of glucose. Sens. Actuat. B-Chem. 2016, 231, 230-238.
DOI Google Scholar
43

Li, L.; Liang, B.; Li, F.; Shi, J. G.; Mascini, M.; Lang, Q. L.; Liu, A. H. Co-immobilization of glucose oxidase and xylose dehydrogenase displayed whole cell on multiwalled carbon nanotube nanocomposite films modified electrode for simultaneous voltammetric detection of D-glucose and D-xylose. Biosens. Bioelectron. 2013, 42, 156-162.
DOI Google Scholar
44

Tanne, J.; Schäfer, D.; Khalid, W.; Parak, W. J.; Lisdat, F. Light-controlled bioelectrochemical sensor based on CdSe/ZnS quantum dots. Anal. Chem. 2011, 83, 7778-7785.
DOI Google Scholar
45

Bergmeyer, H. U. Methods of Enzymatic Analysis; Academic Press: New York, 1974.
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Publication history
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Acknowledgements

Publication history

Received: 28 September 2016
Revised: 14 November 2016
Accepted: 15 November 2016
Published: 21 February 2017
Issue date: June 2017

Copyright

© Tsinghua University Press and Springer-Verlag Berlin Heidelberg 2016

Acknowledgements

Acknowledgements

This work was supported by the Spanish Ministry of Economy and Competitiveness (grant number BIO2014-59741-R).

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