Polymer Dots for Photoelectrochemical Bioanalysis - American

Subscriber access provided by UB + Fachbibliothek Chemie | (FU-Bibliothekssystem)

Article

Polymer Dots for Photoelectrochemical Bioanalysis Yu Li, Nan Zhang, Wei-Wei Zhao, Dechen Jiang, Jing-Juan Xu, and Hong-Yuan Chen Anal. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.analchem.7b00162 • Publication Date (Web): 06 Apr 2017 Downloaded from http://pubs.acs.org on April 7, 2017

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

Analytical Chemistry is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 19

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Analytical Chemistry

Polymer Dots for Photoelectrochemical Bioanalysis Yu Li, Nan Zhang, Wei-Wei Zhao,* De-Chen Jiang,* Jing-Juan Xu and Hong-Yuan Chen State Key Laboratory of Analytical Chemistry for Life Science and Collaborative Innovation Center of Chemistry for Life Science, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, Jiangsu 210023, China

* E-mail: [email protected] * E-mail: [email protected]

ACS Paragon Plus Environment

1


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 2 of 19

ABSTRACT: Different from the most extensively used inorganic quantum dots (Qdots) for the current state-of-the-art photoelectrochemical (PEC) bioanalysis, this work reports the first demonstration of polymer dots (Pdots) for the novel PEC bioanalysis. The semiconducting Pdots was prepared via the reprecipitation method and then immobilized onto the transparent indium tin oxide (ITO) glass electrode for the PEC biodetection of the model molecule L-cysteine. The experimental results revealed that the as-fabricated Pdots exhibited excellent and interesting PEC activity and good analytical performance of rapid response, high stability, wide linear range and excellent selectivity. Especially, the PEC sensor could easily discriminate the L-cysteine from Lglutathione reduced (L-GSH). This work manifested the great promise of Pdots in the field of PEC bioanalysis. And it is believed that our work could inspire the development of numerous functional Pdots with unique properties for the innovative PEC bioanalytical purposes in the future.

KEYWORDS: Photoelectrochemical, Bioanalysis, Polymer dots, Cysteine


2

Page 3 of 19

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Polymer dots (Pdots) have recently emerged as a new family of functional nanomaterials that exhibit extraordinary properties including high brightness, excellent photostability, fast emission rates, and minimal toxicity.1-4 The appeal of Pdots relies on the readily tailored electrical and optical properties of semiconductors combined with the easy process ability of polymers. Their dimensions can be manipulated from a few nanometers to tens of nanometers with different component ratios and sizes, and their corresponding properties and performances could thus be altered easily. Besides, the good biocompatibility and facile surface functionalization of Pdots have made them extremely advantageous for various biological in vitro and in vivo applications. Comparing with the well-known and extensively studied quantum dots (Qdots), however, the Pdots have superior properties in terms of low cytotoxicity and high biocompatibility. The potential leakage of metal ions (e.g., Cd and Se) from the Qdots and the associated cell toxicity are still critical concerns for in vivo QDs-based applications. Especially, the insufficient brightness, the difficulties in tailoring the surfaces of QDs, as well as the stochastic blinking phenomenon might impede their use for many in vivo and photon-starved sensing applications. In addition, the Pdots in principle have the porous structures and thus possess transmissibility for proper-size small molecules. Such structural properties indicate their great potentials in manifold applications. Despite these advantages of Pdots, some hurdles still remain. For example, the serious self-quenching and reabsorption phenomena of polymer fluorescence upon condensation into a Pdot form render the development of bright NIR-emitting Pdots remains a significant challenge. Currently, there has been increasing efforts in exploiting Pdots for various fields such as light-emitting diodes, field-effect transistors, as well as fluorescence probes.5-7 In light of the large two photon absorption cross sections and thus the extraordinary light-gathering power of conjugated polymers, the Pdots might act as efficient


3


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 4 of 19

light-harvesting materials for elegant construction of manifold photoelectrochemical (PEC) chemsensors and biosensors. Unfortunately, such explorations have not been conducted. PEC bioanalysis represents a newly emerged technique that rapidly becoming a subject of hot research interests due to its notable advantages.8-11 Essentially, PEC bioanalysis is the advanced integration of photoelectrochemistry and electrochemical bioanalysis,12-17which endow this new methodology with robustness, low cost, simple instrumentation and high sensitivity.18-23 Previously, to realize exquisite PEC bioanalysis, diverse photoactive material-biomolecule hybrid nanoarchitectures have been explored for specific PEC analytical purposes.24-31 Nevertheless, these works rely intensively upon various QDs and TiO2 based materials, which are often subject to severe problems such as relatively low quantum yields/photo-to-current conversion efficiencies or susceptibilities to photo-bleaching. Obviously, new semiconductive species with novel characteristics are in urgent need for the further advancement of PEC bioanalysis. This work reports the validation of Pdots for the novel PEC bioanalysis, the success of which might pave the way to the implementation of a new cluster of semiconducting species for future PEC bioanalysis development. Scheme 1 shows our approach schematically. We synthesized the Pdots via the reprecipitation method with photosensitizer tetraphenylporphyrin (TPP), poly(styrene-co-maleic anhydride) (PSMA), and the conjugated polymer poly[(9,9dioctylfluorenyl-2,7-diyl)-co-(1,4-benzo-{2,1′,3}-thiadazole)] (PFBT),32 the as-fabricated TPPdoped PFBT Pdots were then immobilized onto the transparent indium tin oxide (ITO) glass electrode with the poly (diallyldimethylammonium chloride) (PDDA) and applied for the PEC biodetection of the model molecule L-cysteine (L-cys), an essential thiol-containing amino acid and the in vivo level of which has been recognized as an important indicator for disease


4

Page 5 of 19

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


diagnosis.25,29,33-35 The experimental results revealed that the Pdots exhibited excellent and interesting PEC activity and the good analytical performance of rapid response, high stability, wide linear range and excellent selectivity. This work reveals the great promise of Pdots for the advanced PEC bioanalysis and has never been reported to our knowledge. Scheme 1. Schematic Illustration for the Preparation of TPP-doped PFBT Pdots and Its Application for the PEC Detection of L-cys

■ EXPERIMENTAL SECTION Reagents and Apparatus. Poly(styrene-co-maleic anhydride) (PSMA) was obtained from Tianjin Heowns Biochem LLC (china)，the conjugated polymer poly[(9,9-dioctylfluorenyl-2,7diyl)-co-(1,4-benzo-{2,1,3}-thiadazole)] (PFBT), the photosensitizer tetraphenylporphyrin(TPP) was obtained from Sigma-Aldrich. Poly (diallyldimethylammonium chloride) (PDDA, 20%, w/w in water, MW=200000-350000), L-cys, ascorbic acid (AA), urea, arginine, glycine, L-citrulline, L-Glutamine, glucose, histidine and L-glutathione reduced was obtained from Sinopharm Chemical Reagent Co., Ltd (China). Other chemicals were of analytical reagent grade and used


5


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 6 of 19

as received. A solution of 0.1 M PBS (pH 7.4) was used to dilute the stock solution when needed. All aqueous solutions were prepared using ultrapure water (Milli-Q, Millipore). PEC measurements were performed with a homemade PEC system equipped with a LED lamp of 450 nm excitation light. Photocurrent was measured on a CHI 660C electrochemical workstation (China) with a three-electrode system: a modified ITO electrode with a geometrical circular area (0.5 cm in diameter) as the working electrode, a Pt wire as the counter electrode and a saturated Ag/AgCl electrode as the reference electrode. Transmission electron microscopy (TEM) was performed with a JEOL model 2000 instrument operating at 200 kV accelerating voltage. Thermo Scientific Varioskan Flash spectral scanning multimode reader were used for absorption spectra and fluorescence measurements in homogeneous assay and membrane phase. Preparation of Pdots. The TPP-doped PFBT nanoparticles were prepared through the reprecipitation method as described previously.32 The PFBT polymer (1 mg/mL), functional polymer PSMA (1 mg/mL), and photosensitizer TPP (1 mg/mL) were dissolved and mixed in THF with a PFBT concentration of 100 µg/mL, a PSMA concentration of 20 µg/mL, and a TPP concentration from 5 µg/mL, respectively. Then, the mixed solution was sonicated to form a homogeneous solution. A total of 10 mL deionized water was sonicated in a bath sonicator while 2 mL of the mixed solution was injected into deionized water quickly. After that, THF was removed by nitrogen stripping and solution was filtered through a 0.22 µm filter. Finally, concentrate the solution by rotary evaporation under 55 ℃. Fabrication of Pdots-ITO Electrode. The TPP-Doped PFBT Pdots modified multilayer film was fabricated by alternately immersing the cleaned ITO slices into a solution of 2% PDDA containing 0.5 M NaCl and the Pdots nanoparticles solution for 10 min, respectively, and this


6

Page 7 of 19

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


process was repeated 5 times to obtain desired photocurrent intensity. The electrodes were carefully washed with doubly distilled water after each dipping step. ■ RESULTS AND DISCUSSION Optical Characterization. The Figure 1 reveals the normalized absorption and emission spectra of the as-fabricated TPP-doped PFBT Pdots. The Pdots exhibited a dominant absorption in the range of 400−500 nm and the doublet peaks were consistent with the initial TPP doping, whereas the emission spectrum presented a red fluorescence (∼660 nm) of the TPP dopant with the fluorescence of PFBT was greatly quenched. This was because that the presence of TPP dopant could considerably quench the donor’s fluorescence due to the combined effects of energy diffusion and energy transfer.36-38 In this work, significantly, the strong absorption in the visible range of 400−500 nm in the spectrum implied its fitness for the employment as photoactive species for the construction of PEC bioanalytical platform, and one may utilize its strong light-harvesting properties and steer the photoactivated excitons as electronic detection signals.8,9 Figure 1 inset shows the photograph and fluorescence image of the TPP-doped PFBT Pdots under a 365 nm UV-lamp.

Figure 1. Normalized absorption and emission spectra of the as-fabricated TPP-doped PFBT Pdots. Inset: The photograph and fluorescence image of the TPP-doped PFBT Pdots under a 365 nm UV-lamp.


7


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 8 of 19

Structural and PEC Characterization. The particle size and morphology of the Pdots were further characterized by transmission electron microscopy (TEM) with the representative image shown in Figure 2. As displayed, the Pdots appeared as quasi-spherical particles and possessed diameters corresponding to ca. 3-4 nm. Such uniform morphology indicated its suitability for the construction of homogeneous photoresponsive films and thus with stable signals. Figure 2 inset depicts the transient photocurrent responses of the Pdots-modified ITO electrode against 1 µM (blue curve) and 20 mM (red curve) L-cys upon the intermittent monochromatic light irradiation. Unexpectedly, the low concentration of L-cys led to a cathodic photocurrent response, whereas the high concentration caused an anodic one.

Figure 2. Typical TEM image of the TPP-doped PFBT Pdots. Inset: the chronoamperometric I−t curves, which were acquired in 0.1 M PBS containing 1 µM (blue) and 20 mM (red) L-cys with 0 V working potential and 450 nm excitation light.

This unique phenomenon should be attributed to the electrochemistry-paved new route of electron transfer for the excitonic Pdots and its thereof interaction with surrounding species. Specifically, upon light excitation, the triplet excited photosensitizer would interact with the dissolved oxygen (3O2) and generate reactive oxygen species (ROS) such as singlet oxygen (1O2). This mechanism has been extensively reported in the field of photodynamic therapy (PDT),


8

Page 9 of 19

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


which associates intimately with the use of photosensitizers to transfer light energy to surrounding oxygen (3O2) to form ROS.39 For the system of Pdots, the conjugated polymer could further efficiently absorb and transfer the excitation energy to the photosensitizer units to generate the singlet oxygen.32 However, as illustrated in Scheme 1, in present case of conducting electronic signal as readout, the yield of the cathodic photocurrent proved beyond doubt that the existence of ITO electrode has opened a new route of electron transfer for the excitonic responses of Pdots, i.e., the transfer of the photogenerated electrons to the ambient oxygen with simultaneous supply of electrons from the electrode to neutralize the holes. However, when in the increased presence of L-cys, as will be revealed by Figure 3A later, it could gradually inhibit the aforementioned process and steer the electron transfer to the electrode. The ejection of the photogenerated electrons to the electrode with the concomitant transfer of electrons from the Lcys would produce the anodic photocurrent. Incidentally, the incident-photon-to-currentconversion efficiency (IPCE) was calculated as 7.02% by the equation: IPCE = (1240 × I)/(λ × Jlight), where I (mA/cm2) is the measured photocurrent density, λ (nm) is the wavelength of incident light, and Jlight (mW/cm2) is power density of the incident light. The storage stability of the Pdots electrode was also tested. After 40 days of storage at 4 °C and under darkness, the electrode exhibited no obvious difference in the photocurrent intensity, demonstrating its good storage stability for further PEC bioanalysis application. The stable responses of the asfabricated and after-storage systems also reflected the excellent film forming ability of the Pdots on the ITO electrodes.


9


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 10 of 19

Figure 3. (A) Photocurrent responses of Pdots/ITO electrode in 0.1 M pH 7.4 PBS in the presence of increasing concentrations of L-cys at the bias voltage of 0V and light wavelength of 450 nm. (B) The stability test against 20 mM L-cys.

Development of the PEC Sensor. The system is then investigated for PEC bioanalysis of L-cys. Figure 3A manifests the typical photocurrents of the Pdots electrode corresponding to variable target concentration. As shown in all photocurrent curves, upon the onset of irradiation, the prompt rise of the signal suggested the fast charge excitation, separation, and transfer in the Pdots and also the rapid response of the Pdots-based PEC system toward the L-cys. The cathodic photocurrent reduction was elevated with the increase of L-cys concentration and changed to the anodic response after 10 mM. The following growth trend of the signal enhancement began to flatten till 40 mM, indicating the near saturation of the target-Pdots reaction. Besides, as shown in Figure 3B, we further performed the photocurrent measurement repeatedly every 10 seconds in the presence of 20 mM L-cys, and the nearly unchanged photocurrent intensity suggested the


10

Page 11 of 19

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


operational stability for signal collection. Incidentally, we further synthesized another PFBT Pdots under the same experimental procedure, with its optical, TEM and PEC characterizations as shown in Figure 4. Comparing Figure 4A with Figure 1 would find the considerably different optical properties, with the sizes of 4-5 nm in Figure 4B as compared to those of 3-4 nm in Figure 2. Consistently, the fluorescence images of the two kinds of Pdots under a 365 nm UVlamp also exhibited different colours of red and yellow. As to the PEC performance, as shown in Figure 4B, even the presence of 100 mM of L-cys could only generate anodic photocurrent of ca. 35 nA, less than that of ca. 40 nA produced by 20 mM L-cys. These preliminary results revealed the intimate relationship between the particle components, sizes and optical/PEC properties.

Figure 4. (A) Normalized absorption and emission spectra of the as-fabricated PFBT Pdots. Inset: The photograph and fluorescence image of the PFBT Pdots under a 365 nm UV-lamp. (B) Typical TEM image of the PFBT Pdots. Inset: the chronoamperometric I−t curves, which were acquired in 0.1 M PBS containing 1 µM (blue) and 100 mM (red) L-cys with 0 V working potential and 450 nm excitation light.


11


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 12 of 19

Analytical Performances. Figure 5A shows the derived calibration curve with the corresponding linear equation as obtained by the linear fitting. As shown, the photocurrent change was proportional to the target concentration logarithmically with the linear range from 1µM to 40 mM and the detection limit was experimentally found as 1µM, which is comparable to some recent reports.40,41 Given the normal concentration of L-cys ranges from 240-360 µM in human plasma,42 these results indicated the present system may suffice for the practical use. By measuring the sample of 60 mM with three electrodes, an intraassay relative standard deviation (RSD) was obtained as 5.9%, implying the good reproductivity. The selectivity of this system was then evaluated by testing common interfering agents including urea, arginine, glycine, Lcitrulline, L-glutamine, glucose, histidine, L-glutathione reduced (L-GSH) and ascorbic acid. As shown in Figure 5B, significantly, the results demonstrated that none of these interferents exhibited anodic response except the target L-cys, implying the excellent selectivity. This interesting phenomenon might be attributed to the ideal match between the properties of L-cys and Pdots. Specifically, among the common electron acceptor (e.g., dissolved oxygen) and electron donors (e.g., ascorbic acid, L-cys and L-GSH), the L-cys is the most prone to PEC oxidation at current conditions. Notably and unexpectedly, the L-GSH here caused an obvious cathodic photocurrent, which was proved to be caused by the acidity of the L-GSH solution. Specifically, with the use of precise pH test paper, the L-GSH dissolution was found to be able to acidize the PBS from pH 7.4 greatly to c.a. pH 6.0. In a control experiment against the pH effects, as shown in Figure 5B inset, the larger cathodic photocurrent at pH 6.0, as compared to that of 7.4, verified that the pH had great effect on the PEC performance of Pdots, the phenomenon of which agreed with previous report of pH-dependent optical performance of Pdots.43 When we further adjusted the pH from 6.0 to neutral value 7.4, as shown in Figure 5B, the proposed Pdots


12

Page 13 of 19

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


system could still discriminate the L-GSH from L-cys, this was due to the different reducibility of two matters and may also due to the affected L-GSH property. Besides, the porous structure of Pdots has transmissibility for small molecules. So, as compared to that of L-GSH, the smaller size of L-cys might also facilitate its diffusion within the Pdots to scavenge the photogenerated holes and hence to contribute to the photocurrent enhancement.44 As to the decreased anodic response of the mixed sample than that of pure L-cys solution, this was caused by the aforementioned L-GSH-induced pH effect against the performance of Pdots in the mixed solution. The feasibility of the proposed system for practical application was evaluated by recovery experiment conducted in the real sample of bee honey. The sample was diluted to specific concentration with a PBS of 7.4, and recovery of the 10 mM and 20 mM L-cys were determined as 93.8 ± 7.3％ and 98.9 ± 7.7％, indicating the applicability of the proposed system for future utilization. As a proof of principle, it is worthy to note that much could be addressed in the Pdots-based PEC bioanalysis in the future research.


13


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 14 of 19

Figure 5. (A) The corresponding linear range. (B) Photocurrent response of Pdots/ITO electrode upon addition of urea, arginine, L-citrulline, glucose, L-glutamine, L-GSH, glycine, histidine, ascorbic acid and L-cys at the same concentrations of 80 mM in 0.1 M PBS (pH 7.4) as well as their mixed sample. Inset: the photocurrent responses of the Pdots electrode against the pH 7.4 (black) and pH 6.0 (red) solutions.

■ CONCLUSIONS In summary, this work has demonstrated the first Pdots-based PEC sensor. Comparing with the commonly used Qdots, the Pdots possess the advantages of good biocompatibility and high processability in terms of surface functionalization, porous structures adjustment, component and size modulation, as well as the corresponding property manipulation. Optical spectroscopic characterizations indicated the strong absorption of Pdots in the visible range, and the chronoamperometric I−t tests revealed the unique photocurrent responses. For the detection of


14

Page 15 of 19

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


model molecule L-cys, it exhibited good analytical performance of rapid response, high stability, wide linear range and excellent selectivity. This work displayed that the Pdots can be a competitive candidate for future PEC bioanalysis development. With other judiciously designed PEC nanobiosystem consisting of alternative Pdots and coupled with specific recognition events,45 the Pdots-based PEC bioanalysis could serve as a general basis for probing numerous other targets of interest. Besides, due to the easy processibility and versatility in surface bioconjugation, such a Pdots-based PEC bioanalysis system might be integrated into various flow-injection systems or microfluidic chips to construct new electronic devices capable of fast, cost-effective and onsite detections. ■ AUTHOR INFORMATION Corresponding Author * E-mail: [email protected] * E-mail: [email protected] Notes The authors declare no competing financial interest. ■ ACKNOWLEDGMENT We thank the National Natural Science Foundation of China (Grant Nos. 21327902, 21305063, 21575060 and 21675080) and the Natural Science Funds of Jiangsu Province (Grant BK20130553) for support. This work was also supported by a Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions. ■ REFERENCES


15


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 16 of 19

(1) Liu, H. Y.; Wu, P. J.; Kuo, S. Y.; Chen, C. P.; Chang, E. H.; Wu, C. Y.; Chan, Y. H. J. Am. Chem. Soc. 2015, 137, 10420-10429. (2) Wang, L.; Fernandez-Teran, R.; Zhang, L.; Fernandes, D. L.; Tian, L.; Chen, H.; Tian, H. Angew Chem. Int. Ed. 2016, 55, 12306-12310. (3) Koner, A. L.; Krndija, D.; Hou, Q.; Sherratt, D. J.; Howarth, M. ACS Nano 2013, 7, 11371144. (4) Wu, C.; Chiu, D. T. Angew. Chem. Int. Ed. 2013, 52, 3086-3109. (5) Zhao, Q.; Zhou, X.; Cao, T.; Zhang, K. Y.; Yang, L.; Liu, S.; Liang, H.; Yang, H.; Li, F.; Huang, W. Chem. Sci. 2015, 6, 1825-1831. (6) Li, S.; Wang, X.; Hu, R.; Chen, H.; Li, M.; Wang, J.; Wang, Y.; Liu, L.; Lv, F.; Liang, X.J.; Wang, S. Chem. Mater. 2016, 28, 8669-8675. (7) Chang, K.; Tang, Y.; Fang, X.; Yin, S.; Xu, H.; Wu, C. Biomacromolecules 2016, 17, 21282136. (8) Zhao, W. W.; Xu, J. J.; Chen, H. Y. Chem. Rev. 2014, 114, 7421-7441. (9) Zhao, W. W.; Xu, J. J.; Chen, H. Y. Chem. Soc. Rev. 2015, 44, 729-741. (10) Freeman, R.; Girsh, J.; Willner, I. ACS Appl. Mater. Interfaces 2013, 5, 2815-2834. (11) Zhou, H.; Liu, J.; Zhang, S. TrAC Trends in Anal. Chem. 2015, 67, 56-73. (12) Zhao, W. W.; Wang, J.; Zhu, Y. C.; Xu, J. J.; Chen, H. Y. Anal. Chem. 2015, 87, 9520-9531. (13) Zhao, W. W.; Yu, X. D.; Xu, J. J.; Chen, H. Y. Nanoscale 2016, 8, 17407-17414. (14) Zhao, W. W.; Xu, J. J.; Chen, H. Y. Analyst 2016, 141, 4262-4271. (15) Tanne, J.; Schafer, D.; Khalid, W.; Parak, W. J.; Lisdat, F. Anal. Chem. 2011, 83, 77787785. (16) Li, Z.; Xin, Y.; Zhang, Z. Anal. Chem. 2015, 87, 10491-10497.


16

Page 17 of 19

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(17) Le Goff, A.; Cosnier, S. J. Mater. Chem. 2011, 21, 3910-3915. (18) Li, Z.; Xin, Y.; Zhang, Z. Anal. Chem. 2015, 87, 10491-10497. (19) Zhu, Y. C.; Zhang, N.; Ruan, Y. F.; Zhao, W. W.; Xu, J. J.; Chen, H. Y. Anal. Chem. 2016, 88, 5626-5630. (20) Li, C.; Wang, H.; Shen, J.; Tang, B. Anal. Chem. 2015, 87, 4283-4291. (21) Li, H.; Mu, Y.; Yan, J. Anal. Chem. 2015, 87, 2007-2015. (22) Tang, J.; Zhang, Y.; Kong, B.; Wang, Y.; Da, P.; Li, J.; Elzatahry, A. A.; Zhao, D.; Gong, X.; Zheng, G. Nano Lett. 2014, 14, 2702-2708. (23) Ma, Z. Y.; Xu, F.; Qin, Y.; Zhao, W. W.; Xu, J. J.; Chen, H. Y. Anal. Chem. 2016, 88, 4183-4187. (24) Wang, L.; Ma, W.; Gan, S.; Han, D.; Zhang, Q.; Niu, L. Anal. Chem. 2014, 86, 1017110178. (25) Long, Y. T.; Kong, C.; Li, D. W.; Li, Y.; Chowdhury, S.; Tian, H. Small 2011, 7, 1624-1628. (26)

Li, J.; Tu, W.; Li, H.; Han, M.; Lan, Y.; Dai, Z.; Bao, J. Anal. Chem. 2014, 86, 1306-

1312. (27) Ma, Z. Y.; Ruan, Y. F.; Xu, F.; Zhao, W. W.; Xu, J. J.; Chen, H. Y. Anal. Chem. 2016, 88, 3864-3871. (28) Dai, H.; Zhang, S.; Hong, Z.; Li, X.; Xu, G.; Lin, Y.; Chen, G. Anal. Chem. 2014, 86, 64186424. (29) Li, R.; Liu, Y.; Cheng, L.; Yang, C.; Zhang, J. Anal. Chem. 2014, 86, 9372-9375. (30) Zhuang, J.; Tang, D.; Lai, W.; Xu, M.; Tang, D. Anal. Chem. 2015, 87, 9473-9480. (31) Wang, J.; Liu, Z.; Hu, C.; Hu, S. Anal. Chem. 2015, 87, 9368-9375.


17


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 18 of 19

(32) Li, S.; Chang, K.; Sun, K.; Tang, Y.; Cui, N.; Wang, Y.; Qin, W.; Xu, H.; Wu, C. ACS Appl. Mater. Interfaces 2016, 8, 3624-3634. (33) Tu, W.; Lei, J.; Wang, P.; Ju, H. Chem. Eur. J. 2011, 17, 9440-9447. (34) Shen, Q.; Jiang, J.; Liu, S.; Han, L.; Fan, X.; Fan, M.; Fan, Q.; Wang, L.; Huang, W. Nanoscale 2014, 6, 6315-6321. (35) Wu, S.; Song, H.; Song, J.; He, C.; Ni, J.; Zhao, Y.; Wang, X. Anal. Chem. 2014, 86, 59225928. (36) Tian, Z.; Yu, J.; Wu, C.; Szymanski, C.; McNeill, J. Nanoscale 2010, 2, 1999-2011. (37) Wu, P. J.; Kuo, S. Y.; Huang, Y. C.; Chen, C. P.; Chan, Y. H. Anal. Chem. 2014, 86, 48314839. (38) Sun, J.; Wang, S.; Gao, F. Langmuir 2016, 32, 12725-12731. (39) Wang, C.; Cui, Q.; Wang, X.; Li, L. ACS Appl. Mater. Interfaces 2016, 8, 29101-29109. (40) Geng, D.; Li, M.; Bo, X.; Guo, L. Sens. Actuators B: Chem. 2016, 237, 581-590. (41) Wang, Y.; Wang, W.; Li, G.; Liu, Q.; Wei, T.; Li, B.; Jiang, C.; Sun, Y. Microchim. Acta 2016, 183, 3221-3228. (42) Seshadri, S.; Beiser, A.; Selhub, J.; Jacques, P. F.; Rosenberg, I. H.; Dagostino, R. B.; Wilson, P. W. F.; Wolf, P. A. N. Engl. J. Med. 2002, 346, 476-483. (43) Chan, Y. H.; Wu, C.; Ye, F.; Jin, Y.; Smith, P. B.; and Chiu, D. T. Anal. Chem. 2011, 83, 1448–1455. (44) Zhan, W. W.; Kuang, Q.; Zhou, J. Z.; Kong, X. J.; Xie, Z. X.; Zheng, L. S. J. Am. Chem. Soc. 2013, 135, 1926-1933. (45) Zhao, W. W.; Xu, J. J.; Chen, H. Y. TrAC Trends in Anal. Chem. 2016, 82, 307-315


18

Page 19 of 19

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


TOC Graphic


19

Polymer Dots for Photoelectrochemical Bioanalysis - American

Recommend Documents