Elsevier

Analytica Chimica Acta

Volume 776, 7 May 2013, Pages 17-23
Analytica Chimica Acta

Fabrication of glucose biosensor for whole blood based on Au/hyperbranched polyester nanoparticles multilayers by antibiofouling and self-assembly technique

https://doi.org/10.1016/j.aca.2013.03.032Get rights and content

Abstract

Acknowledging the benefits of hyperbranched polymers and their nanoparticles, herein we report the design and synthesis of sulfonic acid group functionalized hydroxyl-terminated hyperbranched polyester (H30-SO3H) nanoparticles and their biomedical application. The H30-SO3H nanoparticles were characterized by transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy and proton nuclear magnetic resonance spectroscopy (1H NMR). The good hemocompatibility of H30-SO3H nanoparticles was also investigated by coagulation tests, complement activation and platelet activation. The novel glucose biosensor was fabricated by immobilizing the positively charged Au nanoparticles, H30-SO3H nanoparticles and glucose oxidase (GOx) onto the surface of glassy carbon electrode (GCE). It can be applied in whole blood directly, which was based on the good hemocompatibility and antibiofouling property of H30-SO3H nanoparticles. The biosensor had good electrocatalytic activity toward glucose with a wide linear range (0.2–20 mM), a low detection limit 1.2 × 10−5 M in whole blood and good anti-interference property. The development of materials science will offer a novel platform for application to substance detection in whole blood.

Highlight

  • A novel method for detection of glucose in whole blood has been developed.

  • The method based on antibiofouling and self-assembly technology was investigated.

  • The antibiofouling technique utilized for sensor is significant for diagnostics.

Introduction

The clinical conditions of diabetes mellitus are well known and well understood, yet remain a growing concern as the prevalence of the disease increases worldwide at an alarming rate [1]. Accurate blood glucose values play an especially important role in the diagnosis of diabetes. In principle, blood glucose values should be given in terms of whole blood, but most hospitals and laboratories now measure and report the serum glucose levels. There are two major reasons for this situation. On one hand, the red blood cells have a higher concentration of protein (e.g. hemoglobin) than serum. On the other hand, serum has a higher water content, therefore, more dissolved glucose than it does in whole blood. To convert from whole-blood glucose, multiplication by 1.15 has been shown to generally give the serum/plasma level [2]. However, the test results are influenced by the different model numbers of test instruments and detection reagents, treatment processes of blood samples, factitious operations, especially additional centrifuge and too long measure time from collecting specimen of blood to examination. Meanwhile, it is very difficult to design and prepare a electrochemical biosensor that can be used in whole blood just because the biofouling of electrode surface can be developed by platelet, fibrin and blood cell adhesion in the complex environment of whole blood media. And the biofouling of electrode surface will bring catastrophic damage to the electron transfer between enzyme and electrode redox center.

The use of home glucose meters for the diagnosis of diabetes is not recommended because of their potential for imprecision. Moreover, the blood samples are obtained from fingertip peripheral but not vein, and doped easily with tissue fluid.

The development of nanomaterials for the ultra sensitive detection of biological species has received great attention because of their unique optical, electronic, chemical and mechanical properties. Most studies focus on metal (gold, silver), carbon and conducting polymers that used to prepare nanomaterials such as nanoparticles [3], [4], nanotubes [5], [6] and nanowires [7], [8], [9]. Analysts in this field are always enthusiastic about finding new materials with good biocompatibility to improve the behavior of biosensors [10], [11]. Despite many technological advances in biosensor research and development and the introduction of many different products, glucose biosensors were still performed in serum [12], [13], [14], [15], [16]. The focus of this paper is the development and investigation of antibiofouling properties of new nanostructured architecture for electrochemical glucose biosensors that applied in whole blood directly. The strategy for decorating electrode of glucose biosensor with Au/hyperbranched polyester nanoparticles multilayers that exhibit excellent antibiofouling property was suggested. This robust strategy demonstrates a methodology for the incorporation of actively antibiofouling moieties onto a passively antibiofouling electrode, and thus expands the range of applications of electrochemical glucose biosensors. The fundamental nature of interpenetration of nanotechnology, antibiofouling, and biosensor technology was investigated.

Section snippets

Materials

H30 (Third-generation aliphatic hyperbranched polyester with 24 terminal hydroxyl groups) was obtained from Suzhou HyperT Resin Science & Technology Co. Ltd. and used with further precipitation and purification. Hydrogen tetrachloroaurate (β) trihydrate (HAuCl4·3H2O, 99.9%) was obtained from Alfa Aesar, a Johnson Matthey Company. Glucose oxidase (GOx), ascorbic acid (AA) and uric acid (UA) were obtained from Sigma–Aldrich Co., β-d-(+)-glucose (99%) was from J&K Chemical Co. Inc.

Characterization of H30-SO3H nanoparticles

Hyperbranched polymers composed of densely branched structures adopt compact conformations with a large number of surface reactive groups. The structural formula of the H30-SO3H nanoparticle was shown in Fig. 1(A). As shown in Fig. 1(B), the H30-SO3H nanoparticles were formed. TEM photograph of the nanoparticles showed the average diameter of 210 nm. FTIR spectra of H30 and H30-SO3H nanoparticles were represented in Fig. S1(A). The spectra for H30-SO3H nanoparticles have vibration bands at 1195

Conclusion

Analysts are always enthusiastic about finding new materials with good biocompatibility to improve the behavior of biosensors. In this case, a novel electrochemical biosensor, which can be conveniently applied for accurate quantification of the level of blood glucose with the help of antibiofouling and self-assembly technology, was investigated. To the best of our knowledge, this is the first time that the hyperbranched polymer nanoparticles functionalized by sulfonic acid group have been

Acknowledgments

The work is supported by NSFC (21144002, 81201210), NSFJS (BK2011781), Major Program for the NSFRHEI of Jiangsu Province (12KJA150006), the Priority Academic Program Development of Jiangsu Higher Education Institutions, and Research project of Jiangsu Province (BY2011109).

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