Multi-analyte explosive detection using a fiber optic biosensor

https://doi.org/10.1016/S0003-2670(99)00571-1Get rights and content

Abstract

A fiber optic immunosensor has been developed for simultaneous detection of the most common explosives, 2,4,6,-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). It employs a competitive immunoassay on the antibody-coated fiber optic probes, in which a fluorescent antigen competes with free antigen of unknown concentration for binding sites on the fiber surface. To achieve dual explosive detection, two α-TNT fiber probes and two α-RDX fiber probes are connected in series. The sample is mixed with fluorescent analogs, Cy5-ethylenediamine-trinitrobenzene (Cy5-EDA-TNB) and Cy5-ethylenediamine-RDX hapten (Cy5-EDA-RDH). Inhibition of the maximum signal in the presence of the sample is proportional to the concentration of the explosive. The detection limits for the multi-analyte assays are equivalent (6 ng/ml for both TNT and RDX) to those of the individual assays (5 ng/ml for both TNT and RDX). The standard curves for TNT and RDX represent a linear relationship between percent signal inhibition and the natural logarithm of analyte concentration in the multi-analyte format, as well as in single analyte assays, thus allowing a simple and precise method of quantification. There is minimal cross-reactivity for the two antigens in the multi-analyte immunosensor, so it is also an effective means in analyzing samples containing mixtures of RDX and TNT.

Introduction

Accurate and rapid monitoring of the environment for pollutants has become increasingly important in the last few years. Emphasis on reducing analysis time, sample size and overall cost has resulted in the development of multi-analyte immunosensors for simultaneous detection of multiple antigens. There are numerous approaches that are being actively examined for multi-analyte detection. Most commonly, antibodies or antigens are localized in the same assay zone labeled with distinct labels such as radioactive markers [1], different fluorescent molecules [2], different enzymes [3], colored latex particles [4], or particles of different sizes [5]. However, a loss of sensitivity is usually observed in the multi-analyte format as compared to the single-analyte detection format. The cause is attributable primarily to difficulties in discriminating between the signals generated by the different labels. An alternative approach utilizes spatially separated assay zones applying the same or different labels [6], [7].

The two most commonly found explosives in environmentally contaminated sites are TNT and RDX. Current U.S. EPA methodology for their detection utilizes reverse phase HPLC. Although very accurate, this technique usually requires pre-concentration of the samples, followed by the extraction of the explosive material, resulting in long analysis time and high cost [8], [9], [10]. Moreover, HPLC has been limited to the laboratory only. Recently, commercially available on-site detection kits for explosives have been introduced [11], [12], [13]. Some of these are antibody assays, based on modified versions of an enzyme-linked immunosorbent assay (ELISA). However, several washing steps, significant waste generation, long analysis time, and the higher cost associated with this methodology, restrict the application of such kits.

The need for accurate, on-site, fast and economical monitoring of the environment for contaminants has triggered the development of a variety of portable, easy to operate, low-cost biosensors. The fiber optic biosensor possesses these characteristics. It employs evanescent wave sensing and molecular recognition to specifically detect explosive analytes [14], [15], [16]. Optical fibers, which have the cladding removed from the distal end to form the sensing region, are attached to a small, portable, fiber optic biosensor, the Analyte 2000 [17]. This sensor is capable of monitoring four optical fiber probes simultaneously. This ability permits duplicate analysis for improved reliability and confidence. Field demonstration of the fiber optic biosensor for TNT has been documented [16].

In this study, the fiber optic biosensor [17] and the competitive immunoassay were developed further to detect RDX and then to perform multi-analyte explosive detection. Two fiber probes coated with antibodies against TNT and two fiber probes coated with antibodies against RDX were connected in series, thus creating spatially separated assay zones. A mixture of the two fluoroscent explosive analogs, Cy5-ethylenediamine-RDX hapten (Cy5-EDA-RDH) and Cy5-ethylenediamine-trinitrobenzene (Cy5-EDA-TNB) was run over the fibers in a competitive immunoassay. Initial work demonstrated the need for changing the detergent employed in the buffers [18]. For a multi-analyte sensor to be useful, it must retain the analytical capacity of the individual sensor. Therefore, we compared the performance of the multi-analyte fiber optic immunosensor for simultaneous detection of TNT and RDX to the performance of the fiber optic immunosensor for detection of a single explosive only. Specifically, limit of detection, standard curve characteristics, and cross-reactivity effects were investigated. Our results clearly demonstrated that the individual fiber optic probes can be connected in series to form a multi-analyte immunoassay with minimal cross-reactivity and achieve analytical performance as accurate as that of the single analyte assays.

Section snippets

Materials

N-succinimidyl-4-maleimidobutyrate (GMBS) and 3-mercaptopropyltrimethoxysilane (MTS) were obtained from Fluka. Anti-TNB monoclonal antibodies (α-TNT-Ab, monoclonal antibody no. IgG50359), RDX hapten, and anti-RDX-hapten (RDH) monoclonal antibodies (a-RDH-Ab, monoclonal antibody no. IgG50591) were purchased from Strategic Diagnostics (Newark, DE). Standard solutions of TNT and RDX were purchased from Radian International (Austin, TX). Cy5-EDA-TNB was synthesized as described before [14]. The

TNT detection: single analyte assay

Fig. 1 represents the percent inhibition of the reference signal as a function of TNT concentration (1–1000 ng/ml), after performing competitive immunoassays on anti-TNT fibers employing the fluorescent analog Cy5-EDA-TNB in either DOC or Tween 20. As mentioned earlier, all previously reported work for explosive detection used Tween 20 in the assay buffers but to prevent possible fluorophore aggregation, DOC is the detergent of choice. The limit of detection is defined as the signal value

Discussion

In this paper, individual assays for TNT and RDX employing an ionic detergent were characterized for range and limits of detection. The performance of a multi-analyte assay using the fiber optic immunosensor for the detection of TNT and RDX was compared to the performance of the individual assays. Specifically, limits of detection, standard curve characteristics, and cross-reactivity effects were investigated.

In order to prevent fluorophore aggregation on the fiber surface, the ionic detergent

Acknowledgements

This work was funded by the Environmental Security Technology Certification Program (ESTCP) and by the Security Environmental Research and Development Program (SERDP). The opinions and assertions contained herein are not to be construed as official policy or reflecting the views of the U.S. Navy or Department of Defense.

References (20)

  • S.G. Hadfield et al.

    J. Immunol. Methods

    (1987)
  • J. Frengen et al.

    J. Immunol. Methods

    (1995)
  • U. Narang et al.

    Anal. Biochem.

    (1998)
  • T.F. Jenkins et al.

    Anal. Chim. Acta

    (1994)
  • I.B. Bakaltcheva et al.

    Sensors and Actuators B

    (1998)
  • G.P. Anderson et al.

    Biosens. Bioelectron.

    (1993)
  • S.M. Gow et al.

    Clin. Chem.

    (1986)
  • J. Vuori et al.

    Clin. Chem.

    (1991)
  • M.N. Nanjee et al.

    Clin. Chem.

    (1996)
  • R.P. Ekins et al.

    Trends Biotechnol.

    (1995)
There are more references available in the full text version of this article.

Cited by (74)

  • Emerging biosensing platforms for quantitative detection of exosomes as diagnostic biomarkers

    2021, Coordination Chemistry Reviews
    Citation Excerpt :

    In the following, we discuss the choice of bioreceptors essential for detection of exosomes, and the design of the label-free and label-based detection formats. Table 2 is a summary of representative optical biosensors for detection of exosomes, including SERS, fluorescent and SPR biosensors [199,202–305], while representative colorimetric, electrochemical and microfluidic biosensors are listed in Table 3 [176–179,306–370]. As we introduced above, biochemical and proteomic analysis confirms abundant exosomal biomolecules [371,372].

  • Microfluidic chip coupled with optical biosensors for simultaneous detection of multiple analytes: A review

    2019, Biosensors and Bioelectronics
    Citation Excerpt :

    The fabrication of suitable multiplex devices is of utmost importance for the development of quick, high-throughput, compact miniaturized and low-cost solutions for biomedical diagnosis. Therefore, it has been great enthusiasm in recent years for developing multitarget analysis using parallel single-analyte or simultaneous multianalyte detection, especially in optical biosensor (Bakaltcheva et al., 1999; Faulds et al., 2010; Nyholm, 2005; Srinivasan et al., 2003). Being one of the most commonly reported biosensors, an optical biosensor combines a biorecognition sensing element with an optical signals detection system, measuring changes in light when binding analytes (Douglass et al., 2002).

  • Campylobacter spp. detection in the 21st century: A review of the recent achievements in biosensor development

    2013, Journal of Microbiological Methods
    Citation Excerpt :

    The setup of an Array biosensor is shown schematically in Fig. 2. Since its development, significant progress has been made by using the Array Biosensor for detecting multiple agents such as organophosphates, the naturally occurring protein ricin, the oligomeric protein complex cholera toxin, ochratoxins, staphylococcal enterotoxin B, bacteria, such as Bacillus anthracis, C. jejuni, Shigella flexneri, etc. (Bakaltcheva et al., 1999; Benecky et al., 1998; Edelstein et al., 2000; Ngundi et al., 2005; Ramanathan, 2006; Ramanathan and Simonian, 2007; Rowe-Taitt et al., 2000a,b; Sapsford et al., 2004; Shriver-Lake and Ligler, 2005; Shriver-Lake et al., 2003; Wadkins et al., 1998). For a recent review of Array Biosensors, readers are encouraged to read Ligler et al. (2007).

  • Rapid detection of nitroaromatic and nitramine explosives on chromatographic paper and their reflectometric sensing on PVC tablets

    2011, Talanta
    Citation Excerpt :

    From synthetic mixtures of TNT and HMX in the concentration range of 10–30 mg L−1 of each, having TNT/HMX (w/w) ratios of 1/3, 1/2, 2/3, 1, 2, and 3; the recoveries tested with the proposed method for TNT and HMX were in the range 102–104% and 94–104%, respectively (table not shown), showing quantitative recoveries for both types of mixtures. Given the fact that the two most commonly found explosives in environmentally contaminated sites are TNT and RDX, and that current U.S.-EPA methodology for their detection utilizes reverse-phase HPLC which is laboratory-limited, costly and laborious, often requiring pre-concentration of analytes, the proposed methodology may be a suitable alternative [27]. In this paper spot detection of TNT samples, the reflectance maximum at 546 nm did not shift within the spectra (recorded for every minute) taken between the first and tenth minute.

View all citing articles on Scopus
View full text