Roderick B. Pernites

Electropolymerization molecularly imprinted polymer (E-MIP) SPR sensing of drug molecules: pre-polymerization complexed terthiophene and carbazole electroactive monomers.

A novel chemosensitive ultrathin film with high selectivity was developed for the detection of naproxen, paracetamol, and theophylline using non-covalent electropolymerized molecular imprinted polymers (E-MIP). A series of monofunctional and bifunctional H-bonding terthiophene and carbazole monomers were compared for imprinting these drugs without the use of a separate cross-linker. A key step is the fast and efficient potentiostatic method of washing the template, which facilitated enhanced real-time sensing by surface plasmon resonance (SPR) spectroscopy. Various surface characterizations (contact angle, ellipsometry, XPS, AFM) of the E-MIP film verified the templating and release of the drug from the cross-linked conducting polymer film.

Superhydrophobic Colloidally Textured Polythiophene Film as Superior Anticorrosion Coating

In this paper, we demonstrated for the first time the use of electrodeposited superhydrophobic conducting polythiophene coating to effectively protect the underlying steel substrate from corrosion attack: by first preventing water from being absorbed onto the coating, thus preventing the corrosive chemicals and corrosion products from diffusing through the coating, and second by causing an anodic shift in the corrosion potential as it galvanically couples to the metal substrate. Standard electrochemical measurements revealed the steel coated with antiwetting nanostructured polythiophene film, which was immersed in chloride solution of different pH and temperature for up to 7 days, is very well protected from corrosion evidenced by protection efficiency of greater than 95%. Fabrication of the dual properties superhydrophobic anticorrosion nanostructured conducting polymer coating follows a two-step coating procedure that is very simple and can be used to coat any metallic surface.

Superhydrophobic–Superoleophilic Polythiophene Films with Tunable Wetting and Electrochromism

IO N There is much interest in superhydrophobic surfaces, as inspired by the non-wetting properties of the lotus leaf. [ 1 ] It can give a water contact angle greater than 150 ° with only 2–3% of the water droplet coming into contact with its surface, which is a common test for designating synthetic superhydrophobic surfaces. [ 1 ] The high water repellency is well worth mimicking because of the myriad industrial and practical applications, namely self-cleaning coatings, antifouling marine coatings, microfl uidics, antibiofouling, and anti-ice adhesion properties. [ 2 ] Here we report a novel and facile preparation of a nonfl uorinated superhydrophobic–superoleophilic polythiophene coating with reversibility to a superhydrophilic-and-oleophobic surface via electrochemical polymerization on a 2D layered colloidal particle template. Interestingly, such fi lms exhibit both simultaneous reversible electrochromic and extreme wettability properties by simply changing the voltage (potential) ex situ. Such a reversible wettability property can result in highly controlled wetting behavior with possible dual applications in self-cleaning coatings, channeling of fl ow properties, controlled membrane separations, and regenerable surfaces together with electro-optical functionality (electrochromic) by a mere switch of the applied potential. Artifi cial superhydrophobic surfaces can be accomplished by developing a dual-scale roughness structure and tuning of surface energy. [ 3 ] Most reports [ 2 , 3 ] have been on synthetic superhydrophobic surfaces fabricated using fl uorinated polymers and small molecule compounds, which are markedly known as low-surface-energy coating materials. [ 4 ] Fluorinated small molecule compounds in particular are more expensive and deemed to have some detrimental effects with bioaccumulation to the environment. [ 5 , 6 ] Therefore, these concerns necessitate the development of nonfl uorinated superhydrophobic coatings with other inherently useful functionality or properties. [ 7 , 8 ]

Patterned surfaces combining polymer brushes and conducting polymer via colloidal template electropolymerization.

Recently, there has been a signifi cant interest in the fabrication of patterned polymer surfaces because of potential applications in surface-based technologies such as microfl uidic devices, chemical/biosensors, platforms for tissue engineering, etc. [ 1 ] To date, polymer brushes are widely used in patterning surfaces due to their robustness, broad range of chemical and mechanical properties, and ability to modify surface properties, [ 2 ] and thus an ideal surrogate for self-assembled monolayers (SAM)s. Despite the numerous applications of patterned polymer surfaces, there have been a limited number of strategies reported toward the formation of laterally well-defi ned binary composition patterned brushes. [ 3 ] Most of the methods used involve expensive, tedious and complex lithographic techniques, [ 4 ]

Electropolymerized Molecularly Imprinted Polymer Films of a Bis-Terthiophene Dendron: Folic Acid Quartz Crystal Microbalance Sensing

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.

Detection of 2,4-dinitrotoluene (DNT) as a model system for nitroaromatic compounds via molecularly imprinted short-alkyl-chain SAMs.

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.

Colloidally Templated Two-Dimensional Conducting Polymer Arrays and SAMs: Binary Composition Patterning and Chemistry

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.

PVK/MWNT Electrodeposited Conjugated Polymer Network Nanocomposite Films

The facile preparation of poly (N-vinyl carbazole) (PVK) and multiwalled carbon nanotubes (MWNTs) solution and conjugated polymer network (CPN) nanocomposite film is described. The stable solutions of PVK/MWNT were prepared in mixed solvents by simple sonication method, which enabled successful deaggregation of the MWNTs with the polymer matrix. MWNT was most effectively dissolved in N-cyclohexyl-2-pyrrolidone (CHP) compared to other solvents like N-methyl pyrrolidone (NMP), dimethyl formamide, and dimethyl sulfoxide (DMSO). The composite solution was relatively stable for months with no observable precipitation of the MWNTs. Thermogravimmetric analysis (TGA) revealed the thermal stability of the nanocomposite while the differential scanning calorimetry (DSC) showed an increasing melting (T(m)) and glass transition (T(g)) temperatures as the fraction of the MWNTs in the nanocomposite was increased. Cyclic voltammetry (CV) allowed the electrodeposition of the nanocomposite film on indium tin oxide (ITO) substrates and subsequent cross-linking of the carbazole pendant group of the PVK to form CPN films. Ultraviolet-visible (UV-vis), fluorescence, and Fourier transform infrared (FTIR) confirmed film composition while atomic force microscopy (AFM) revealed its surface morphology. Four-point probe measurements revealed an increase in the electrical conductivity of the CPN nanocomposite film as the composition of the MWNTs was increased: 5.53 × 10(-4) (3% MWNTs), 0.53 (5%), and 1.79 S cm(-1) (7%). Finally, the interfacial charge transfer resistance and ion transport on the CPN nanocomposite film was analyzed by electrochemical impedance spectroscopy (EIS) with a measured real impedance value of ∼48.10 Ω for the 97% PVK and 3% MWNT ratio of the CPN nanocomposite film.

Facile approach to graphene oxide and poly(N-vinylcarbazole) electro-patterned films

A facile approach of making scalable nanocomposite and electro-patterned films using graphene oxide (GO) and poly(N-vinylcarbazole) (PVK) is reported. The method involves the layering of polystyrene colloidal templates, electrodeposition of the composite film on template array, and finally removal of the sacrificial templates to reveal the patterned GO-PVK arrays.

Interfacial Behavior of OEG–Linear Dendron Monolayers: Aggregation, Nanostructuring, and Electropolymerizability

We report on the interesting interfacial behavior of oligoethylene glycol or OEGylated linear dendron monolayers at the air-water interface as a function of (a) carbazole dendron generation, (b) the length of the OEG units, and (c) the surface pressure applied upon compression. Surface pressure-area isotherms, hysteresis studies, and isobaric creep measurement revealed a structure-property relationship consistent with the hydrophilic-lipophilic balance of a linear dendron with the OEG group serving as the surface anchor to the water subphase. AFM studies revealed that all the OEGylated carbazole dendrons self-assemble into spherical morphology at low surface pressures but form ribbonlike structures as the surface pressure is increased. This nanostructuring is primarily imparted by the increase in van der Waals forces with increasing amount of carbazole units per dendron generation on a hydrophilic mica surface. Further, electrochemical cross-linking of the carbazole molecules by cyclic voltammetery (CV) on doped Si wafer has enabled the formation of an LB film monolayer with a secondary level of organization in the monolayer imparted by the inter- and intramolecular cross-linking among the carbazole units. This study should provide a basis for monolayer film materials based on combining the LB technique and electrochemical cross-linking for nanostructuring superstructures at the air-water interface.