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Printed Highly Ordered Conductive Polymer Nanowires Doped with Biotinylated Polyelectrolytes for Biosensing Applications

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The demand for fast and ultratrace biomarkers detection is increasing in bioanalytical chemistry. In this work, highly ordered nanowires array and sensor integration are achieved with nanoscale printing approach. Negatively charged poly(3,4‐ethylenedioxythiophene)–poly(styrenesulfonate) doped with positively charged PEGylated biotin‐derivatized polyelectrolytes results a direct biofunctionalization on the nanowire surface without multiple postmodification steps. It provides homogeneous dispersed biofunctional sites and nonfouling surface on the nanowires. The ordered nanowires array enables the immunosensor to detect biotargets quickly and ultrasensitively. The nanowires impedimetric immunosensor is demonstrated for specific biomarkers detection and achieved a minimum responsive concentration as low as 10 pg mL−1 for protein biomarker and 10 CFU mL−1 for pathogen. A kind of biotin functionalization ink is achieved by doping with PEGylated biotin‐derivatized polyelectrolytes which enables a direct biofunctionalization on the nanowire surface. Then an immunosensor based on highly ordered nanowires array is fabricated by nanoscale printing approach. This sensor can be a general platform for different materials and various bioanalytical applications with ultrahigh sensitivity, trace detection, and fast response.
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1900671 (1 of 9) © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Printed Highly Ordered Conductive Polymer Nanowires
Doped with Biotinylated Polyelectrolytes for Biosensing
Applications
Qiannan Xue, Qikun Wang, Ziyu Han, Ning Tang, Cheng Zhou, Wenwei Pan,
Yanyan Wang, and Xuexin Duan*
DOI: 10.1002/admi.201900671
interests, the high fabrication cost, compli-
cated constructions of the device, and mul-
tiple functionalization steps hinder their
incorporation into real applications.[8] In
general, there are two strategies to fabricate
nanowire devices: top down approach uses
conventional lithography (e.g., e-beam)
to fabricate the required nanostructures
which can make homogeneous nanowires
array however it is suffered by the high
fabrication cost and material limitations.
Bottom up approaches construct the sen-
sors using chemical synthesized nanowires
as building blocks which are typically
driven by self-assembly.[9] Since the nano-
wires are very small in size, it is very dif-
ficult to achieve repeatable devices with
highly ordered nanowires. There is an urgent need to develop
low-cost, simple, and reliable approach for nanowire device
preparation.[10] Alternative nanoscale lithography approach
featured with cost-effectiveness has been developed to fabricate
nanowires, which triggered a lot research interests.[11]
Very recently, we developed a nanoscale printing approach
which uses aqueous solution of conductive polymers as inks.
Highly ordered nanowires could be printed on various sub-
strates through imprinted soft nanomold at a relatively low
cost and without the requirement of cleanroom facilities.[12]
Such techniques have been successfully applied to fabricate
nanowires based chemresistive type of gas sensors for volatile
organic compounds (VOC) detection.[13] In this work, we
applied this approach to fabricate impedimetric biosensor based
on highly ordered biotin doped conductive polymer nanowires
array. Particularly, we developed biofunctional nanomaterials
as inks direct for nanowires fabrication and functionalization,
which is a key part of the nanoscale biosensor preparation.
Existing methods generally require multiple surface function-
alization steps, which may bring uncertainties. Stability of
functional groups on nanowires is crucial for the performance
of biosensor. Here, the biofunctional groups were directly car-
ried on the nanowires surface by doping the conductive poly-
mers with PEGylated biotin-derivatized polyelectrolytes which
enables a direct biofunctionalization on the nanowire surface
with high repeatability and less biofouling and avoids the mul-
tiple postsurface functionalization steps. After conjugation with
streptavidin (SAv) and biotinylated antibodies, the fabricated
The demand for fast and ultratrace biomarkers detection is increasing in
bioanalytical chemistry. In this work, highly ordered nanowires array and
sensor integration are achieved with nanoscale printing approach. Nega-
tively charged poly(3,4-ethylenedioxythiophene)–poly(styrenesulfonate)
doped with positively charged PEGylated biotin-derivatized polyelectrolytes
results a direct biofunctionalization on the nanowire surface without multiple
postmodification steps. It provides homogeneous dispersed biofunctional
sites and nonfouling surface on the nanowires. The ordered nanowires array
enables the immunosensor to detect biotargets quickly and ultrasensitively.
The nanowires impedimetric immunosensor is demonstrated for specific bio-
markers detection and achieved a minimum responsive concentration as low
as 10 pg mL1 for protein biomarker and 10 CFU mL1 for pathogen.
Dr. Q. Xue, Q. Wang, Z. Han, Dr. N. Tang, C. Zhou, W. Pan, Dr. Y. Wang,
Prof. X. Duan
State Key Laboratory of Precision Measuring Technology
and Instruments
School of Precision Instruments and Optoelectronics Engineering
Tianjin University
Tianjin 300072, China
E-mail: xduan@tju.edu.cn
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/admi.201900671.
Nanowires
1. Introduction
In recent years, there is large demand for developing biosensing
devices with high sensitivity, low power assumption, low-cost,
user-friendliness, and rapid diagnosis.[1] Nanoscale biosensors
integrated with specific interactions (e.g., antigen–antibody reac-
tions) could provide stable and excellent selectivity which have
been largely applied for bioanalytical chemistry.[2] Due to the
rapid development of nanotechnology, nanoscale transducers
(e.g., nanotubes, nanowires, nanoparticles, etc.) have been widely
used in various biosensors.[3] Among all these nanostructures,
1D nanotransducers,[4] such as nanowires[5] and nanofibers[6]
are considered as the most promising structures for realizing
ultrasensitive biosensing because of their high surface-to-
volume ratio and less steric hindrance for capture the targets.[7]
Though nanowires based sensors have triggered many research
Adv. Mater. Interfaces 2019, 6, 1900671
... Commercially available conductive polymers such as poly (3, 4-ethylenedioxythiophene)-poly (styrenesulfonate) (PEDOT:PSS) are doped with PEGlated biotin-derivatized polyelectrolytes and printed on the nanowire surface, as shown in Figure 5i. This highly ordered nano-array setup could detect E. coli as low as 10 CFU/mL [167]. Rolling circle amplification (RCA) is a powerful method for DNA amplification, and the authors employed the technique to enhance the detection sensitivity of E. coli O157:H7 in the microfluidic system. ...
... As stated above, detection systems for infectious pathogens have started exploring the potential application of smart materials to develop robust and high throughput technology. A brief summary of the emerging smart materials for microbial pathogens is shown in Table 3. [161] (iv) Wide detection array (v) Relatively large bandwidth terfaces (iv) Tunability of the slowdown factor in given structure Ionic Liquid based systems (i) Both conductor and binder (ii) Good catalytic ability and super sensitivity (iii) High thermal stability (i) Relatively expensive as compared to conventional organic solvents (ii) High cytotoxicity (iii) Mostly limited to electro-analytical system 10 2 CFU/mL [163] 10 3 CFU/mL [164] Responsive Polymer based system (i) Multifunctionality (ii) Structural stability (iii) Facile integration in the detection devices (iv) Tunable detection sensitivity (i) Tedious synthesis process of the designed responsive polymer (ii) Lack of toxicity data profile 10 CFU/mL [167] 10 2 CFU/mL [168] Figure 5. Responsive polymer-based pathogen detection system. (i) (a) Fabrication steps of the immunosensor using conductive polymers such as PEDOT:PSS, and (b) immobilization and detection strategies of E. coli using the nanoarray setup. ...
Article
Full-text available
The development of robust bioanalytical devices and biosensors for infectious pathogens is progressing well with the advent of new materials, concepts, and technology. The progress is also stepping towards developing high throughput screening technologies that can quickly identify , differentiate, and determine the concentration of harmful pathogens, facilitating the decision making process for their elimination and therapeutic interventions in large-scale operations. Recently, much effort has been focused on upgrading these analytical devices to an intelligent technological platform by integrating them with modern communication systems, such as the internet of things (IoT) and machine learning (ML), to expand their application horizon. This review outlines the recent development and applications of bioanalytical devices and biosensors to detect pathogenic microbes in environmental samples. First, the nature of the recent outbreaks of pathogenic microbes such as foodborne, waterborne, and airborne pathogens and microbial toxins are discussed to understand the severity of the problems. Next, the discussion focuses on the detection systems chronologically, starting with the conventional methods, advanced techniques, and emerging technologies, such as biosensors and other portable devices and detection platforms for pathogens. Finally, the progress on multiplex assays, wearable devices, and integration of smartphone technologies to facilitate pathogen detection systems for wider applications are highlighted .
... One example is a PEGylated biotin derivative that was further functionalized with antibodies for selective detection of E. coli. 174,199 For other CPs, the use of various kinds of additional property modifiers including ions, (bio)molecules, or nanomaterials is considered more straightforward as it does not alter physical and chemical properties as much as functionalization through chemical reactions. For example, boronic acid derivatives such as 3-aminophenylboronic acid (3-APBA) and 4-N-pentylphenylboronic acid (PBA) as postfunctionalization adjuvants have been reported to have provided binding affinity to the electronegative diol groups on bacterial cell walls. ...
... Multiple steps were followed in the sensor design, including doping the PEDOT:PSS with PEGylated biotinderivatized polyelectrolytes for homogeneous dispersion of functional sites and to prevent biofouling on the surface of the nanowires, see Figure 18a−d; postfunctionalization with streptavidin and biotinylated antibodies allowed for selective immune sensing. 174 Device performance was tested to detect the different concentrations of E. coli ranges of 10−10 6 CFU/ mL only after 10 min of incubation (Figure 18c,d). For the sensing of pathogens, the device structure played a significant role in achieving high sensitivity toward small changes in pathogen concentration down to 10 CFU/mL with micrometer-scale spacing between nanowires that enable detection of small variations in impedance signal. ...
... The semi-conducting nanowires can be used for label-free and direct detection of analytes [237,238]. Various types of nanowires have been explored for sensing application such as silver nanowires [239], silica nanowires [240,241], polymer nanowires [242,243], and metal oxide nanowires [244]. Nanowires have been investigated for label-free and direct detection of biomolecules such as DNA [245][246][247], biomarkers [248,249], proteins [250][251][252], and pathogens [253][254][255]. ...
Chapter
Personalized medicine, also known as precision medicine, redefines current clinical practice by altering treatments to account for patient heterogeneity that collectively results from genetic, phenotypic, or psychologic variation. This concept dispenses with the “one size fit all” treatment regimen of traditional medicine and instead embraces the requirement for personalized care tailored to an individual’s specific healthcare needs. Nanotechnology is used in conjunction with advanced tools such as genomics, metabolomics, and proteomics to achieve more personalized therapeutic, diagnostic, and theranostic strategies. The chapter first introduces the transformative concept of personalized medicine, as well as the omics tools that serve as the critical driving forces for this paradigm. The chapter transitions to describe and discuss breakthrough advances in nanotechnology, with specific emphasis on commonly employed nanoparticles and nanostructures, for enhancing the clinical practice of personalized medicine.
... The semi-conducting nanowires can be used for label-free and direct detection of analytes [237,238]. Various types of nanowires have been explored for sensing application such as silver nanowires [239], silica nanowires [240,241], polymer nanowires [242,243], and metal oxide nanowires [244]. Nanowires have been investigated for label-free and direct detection of biomolecules such as DNA [245][246][247], biomarkers [248,249], proteins [250][251][252], and pathogens [253][254][255]. ...
Chapter
Personalized medicine, also known as precision medicine, redefines current clinical practice by altering treatments to account for patient heterogeneity that collectively results from genetic, phenotypic, or psychologic variation. This concept dispenses with the “one size fit all” treatment regimen of traditional medicine and instead embraces the requirement for personalized care tailored to an individual’s specific healthcare needs. Nanotechnology is used in conjunction with advanced tools such as genomics, metabolomics, and proteomics to achieve more personalized therapeutic, diagnostic, and theranostic strategies. The chapter first introduces the transformative concept of personalized medicine, as well as the omics tools that serve as the critical driving forces for this paradigm. The chapter transitions to describe and discuss breakthrough advances in nanotechnology, with specific emphasis on commonly employed nanoparticles and nanostructures, for enhancing the clinical practice of personalized medicine.
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