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ABSTRACT: An innovation to thin-film molecular imprinting is presented for the sensitive detection and effective discrimination of chiral compounds using a portable quartz crystal microbalance transduction technique. The facile approach involves i) colloidal sphere layering of latex particles onto the surface via a Langmuir-Blodgett-like technique followed by ii) template molecular imprinting using electrodeposition of a single functional and cross-linking monomer.
Small 03/2012; 8(11):1669-74. · 8.35 Impact Factor
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ABSTRACT: Bisphenol A (BPA) sensing was investigated based on electrochemical impedance spectroscopy (EIS) measurements of an electropolymerized molecularly imprinted polymer (E-MIP) film. The E-MIP film is composed of varying ratios of BPA–terthiophene and carbazole monomer complex deposited onto indium tin oxide (ITO) substrates via anodic electropolymerization using cyclic voltammetry (CV). Subsequently, the interfacial properties of these films were studied using the non-Faradaic EIS technique. The same technique was then used to measure the presence of templated BPA which is a known endocrine disrupting chemical (EDC). Analyses of the EIS results were performed using equivalent circuits in order to model the electrical and impedance properties through the interface. A linear calibration curve was established in the range 0–12 mM concentrations of the analyte. Moreover, the selectivity of the films against bisphenol AF and diphenolic acid was demonstrated. The E-MIP sensor may have advantages in environmental monitoring of bisphenol A in aqueous analyte/pollutant samples.
08/2011;
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ABSTRACT: A 2-D molecularly imprinted monolayer (2-D MIM) approach was used to prepare a simple and robust sensor for nitroaromatic compounds with 2,4-dinitrotoluene (DNT) as the model compound, which is a precursor and analog for explosive 2,4,6-trinitrotoluene (TNT). In contrast to studies utilizing long-chain hexadecylmercaptan self-assembled monolayers (SAM)s for sensing, a shorter-chain alkylthiol (i.e., butanethiol SAM) was utilized for DNT detection. The role of the chain length of the coadsorbed alkylthiol was emphasized with a matched template during solution adsorption. Semiempirical PM3 quantum calculations were used to determine the molecular conformation and complexation of the adsorbates. A switching mechanism was invoked on the basis of the ability of the template analyte to alter the packing arrangement of the alkylthiol SAMs near defect sites as influenced by the DNT-ethanol solvent complex. A 2-D MIM was formed on the Au surface electrode of a quartz crystal microbalance (QCM), which was then used to sense various concentrations of the analyte. Interestingly, the 2-D MIM QCM also enabled the selective detection of DNT even in a mixed solution of competing molecules, demonstrating the selectivity figure of merit. Likewise, electrochemical impedance spectroscopy (EIS) data at different concentrations of DNT confirmed the 2-D MIM effectiveness for sensing based on the interfacial conformation and electron-transport properties of the imprinted butanethiol SAM.
Langmuir 06/2011; 27(11):6768-79. · 4.19 Impact Factor
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Advanced Materials 06/2011; 23(28):3207-13. · 13.88 Impact Factor
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ABSTRACT: A facile approach for enabling or inhibiting the adsorption of protein and adhesion of bacterial cells on a potential-induced reversibly wettable polythiophene film is described. The superhydrophobic polymeric surface was first prepared by a two-step process that combines the layering of polystyrene (PS) latex particles via a Langmuir–Blodgett (LB)-like technique followed by cyclic voltammetric (CV)–electrodeposition of polythiophene from a terthiophene ester monomer. The polythiophene conducting polymer coating enabled control of the wettability of the surface by simply changing its redox property via potential switching. The influence of morphology on this switching behavior is also described. The wettability in return controls the adsorption of protein and adhesion of bacterial cells. For instance, the undoped polythiophene film, which is superhydrophobic, inhibits the adhesion of fibrinogen proteins and Escherichia coli (E. coli) cells. On the other hand, the doped film, which is hydrophilic, leads to increased attachment of both protein and bacteria. Unlike most synthetic antiwetting surfaces, the as-prepared superhydrophobic coating is nonfluorinated. It maintains its superhydrophobic property at a wide range of pH (pH 1–13) and temperature (below −10 °C and between 4 and 80 °C). Moreover, the surface demonstrated self-cleaning properties at a sliding angle as low as 3° ± 1. The proposed methodology and material should find application in the preparation of smart or tunable biomaterial surfaces that can be either resistant or susceptible to proteins and bacterial cell adhesion by a simple potential switching.Keywords: superhydrophobic; polythiophene; polystyrene particles; electropolymerization
05/2011;
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Advanced Materials 03/2011; 23(10):1287-92. · 13.88 Impact Factor
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ABSTRACT: A facile approach and strategy toward binary-composition, two-dimensional (2D) patterned surfaces of conducting polymer periodic arrays, together with thiol self-assembled monolayers (SAMs) is described. The method involved a Langmuir-Blodgett (LB)-like deposition of latex microsphere particles, electropolymerization via cyclic voltammetric (CV) techniques, and self-assembly of an amphiphile. The LB-like technique enabled the monolayer deposition of different sizes of polystyrene (PS) particles in hexagonal packing arrangement on planar substrates. Combining the LB-like method with CV electropolymerization is advantageous because it provides deposition control of a polymer interconnected network, controlled composition ratio of polymer and SAMs, and control of 2D size and spacing of the spherical void pattern. Electrochemical-quartz crystal microbalance (EC-QCM) in situ monitoring of the film deposition quantified a constant and linear growth rate, with varying viscoelastic behavior of the conducting polymer adsorption on planar and PS-templated substrates. The dual-patterned surface provided a good imaging contrast as observed by atomic force microscopy (AFM). Complementary analyses such as X-ray photoelectron spectroscopy (XPS), attenuated total internal reflection infrared (ATR IR) spectroscopy, ultraviolet-visible (UV-vis) spectroscopy, and static contact angle measurements were used to characterize the formation of the patterned surface. The versatility of the method enables the potential for making various types of quantitative binary compositions and patterned surfaces using different combinations of conducting polymer or functional SAMs, which can be extended in the future to polymer brushes and layer-by-layer assembly of various materials.
ACS Applied Materials & Interfaces 02/2011; 3(3):817-27. · 4.53 Impact Factor
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ABSTRACT: A facile approach to tailor-made, highly selective, and robust ultrathin sensor film for theophylline detection was demonstrated by an electropolymerized molecularly imprinted polymer (E-MIP) film of a terthiophene derivative. The method involved direct electropolymerization of the H-bond complexing terthiophene monomer. A key enabling step in sensor fabrication is the use of an electrochemically mediated washing step of the template. The formation of the E-MIP film was monitored by in situ electrochemical surface plasmon resonance (EC-SPR) spectroscopy, allowing real-time observation of the simultaneous changes in electrochemical and optical properties of the film. Surface characterization techniques for the electropolymerized films include atomic force microscopy (AFM), ellipsometry, static contact angle, X-ray photoelectron spectroscopy (XPS), and quartz crystal microbalance (QCM). A linear calibration curve (R = 0.994) of the E-MIP/SPR sensor for theophylline detection was obtained with a 10−50 μM−1 range and a limit of detection (LOD) of 3.36 μM−1. The fabricated E-MIP sensor film showed a homogeneous surface coverage, high sensitivity, long-term stability, and strong selectivity toward the imprinted template molecule. This indicated the formation of precise and stable cavities that retained the exact memory of the size, shape, and orientation of the functional groups during the templating electropolymerization steps.
11/2010;
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ABSTRACT: In this study, a series of electrochemically active oligo(ethylene glycol) (OEG) linear-dendrons have been synthesized and grafted onto electrode surfaces by cyclic voltammetry (CV) to improve protein resistance. Dendronized molecules with peripheral carbazole functionality and branching architecture enabled tethering of the poly(ethylene glycol) (PEG) or OEG group with a predictable number of electrochemical reactive groups affecting OEG distribution and orientation. It is possible that ample spacing between the OEG chains affects the intrinsic hydration of these layers and thus surface protein resistance. The films were characterized by CV, surface plasmon resonance (SPR), static contact angle measurements, and atomic force microscopy (AFM). This approach should enable improved nonbiofouling properties on biorelevant electrode surfaces (metal or metal oxides) by potentiostatic or potentiodynamic electrochemical methods, providing an alternative to the self-assembled monolayer (SAM) approach for anchoring PEG layers.
ACS Applied Materials & Interfaces 11/2010; 2(12):3401-5. · 4.53 Impact Factor
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ABSTRACT: A folic acid sensor was prepared via an electropolymerized molecularly imprinted polymer (E-MIP) film of a bis-terthiophene dendron on a quartz crystal microbalance (QCM). The cyclic voltammetry (CV) electrodeposition of the imprinted polymer film was monitored by electrochemical QCM or E-QCM, enabling in situ monitoring and characterization of E-MIP film formation and the viscoelastic behavior of the film. A key component of the E-MIP process is the use of a bifunctional monomer design to precomplex with the template and function as a cross-linker. The complex was electropolymerized and cross-linked by CV to form a polythiophene matrix. Stable cavities were formed that specifically fit the size and shape of the folic acid template. The same substrate surface was used for folic acid sensing. The predicted geometry of the 1:2 folic acid/terthiophene complex was obtained through semiempirical AM1 quantum calculations. The analytical performance, expressed through the figures of merit, of the sensor in aqueous solutions of the analyte was investigated. A relatively good linearity, R(2) = 0.985, was obtained within the concentration range 0-100 μM folic acid. The detection limit was found to be equal to 15.4 μM (6.8 μg). The relative cross selectivity of the folic acid imprinted polymer against the three molecules follows this trend: pteroic acid (= 50%) > caffeine (= 41%) > theophylline (= 6%). The potential and limitations of the E-MIP method were also discussed.
ACS Applied Materials & Interfaces 11/2010; 3(2):191-203. · 4.53 Impact Factor
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ABSTRACT: The fabrication and characterization of poly(vinylcarbazole) (PVK)-conjugated polymer network (CPN) anticorrosion coatings on flat surfaces, steel coupons or indium tin oxide (ITO) glass substrates, is reported. Electrochemical deposition methods (potentiostatic and potentiodynamic) were employed by anodic oxidation of the carbazole side units in the PVK chains, resulting in electrodeposition of a cross-linked or network macromolecular structure. This is different from traditional conjugated polymer (CP) coatings made up of mostly linear species derived from direct electropolymerization of small molecule monomers. The coating composition was characterized by attenuated total reflection infrared spectroscopy (ATR-IR) and photoelectron spectroscopy (XPS). Atomic force microscopy (AFM) allowed morphological comparison between the coatings in terms of deposition technique and surface roughness. Electrochemical impedance spectroscopy (EIS) was subsequently carried out on PVK-coated steel coupons to evaluate the performance of such coatings in an accelerated corrosion environment. The deviation from the ideal (i.e., perfectly dielectric) capacitor-like behavior and Bode plot data suggested that the CPN approach of electrodeposited PVK coatings resulted in very good protection against weathering of engineering metals.
09/2010;
