Nanobiosensing with graphene and carbon quantum dots: Recent advances.

Graphene and carbon quantum dots (GQDs and CQDs) are relatively new nanomaterials that have demonstrated impact in multiple different fields thanks to their unique quantum properties and excellent biocompatibility. Biosensing, analyte detection and monitoring wherein a key feature is coupled molecular recognition and signal transduction, is one such field that is being greatly advanced by the use of GQDs and CQDs. In this review, recent progress on the development of biotransducers and biosensors enabled by the creative use of GQDs and CQDs is reviewed, with special emphasis on how these materials specifically interface with biomolecules to improve overall analyte detection. This review also introduces nano-enabled biotransducers and different biosensing configurations and strategies, as well as highlights key properties of GQDs and CQDs that are pertinent to functional biotransducer design. Following relevant introductory material, the literature is surveyed with emphasis on work performed over the last 5 years. General comments and suggestions to advance the direction and potential of the field are included throughout the review. The strategic purpose is to inspire and guide future investigations into biosensor design for quality and safety, as well as serve as a primer for developing GQD- and CQD-based biosensors.

Highly Luminescent Heavier Main Group Analogues of Boron-Dipyrromethene.

The preparation and photophysical properties of two heavier main group element analogues of boron-dipyrromethene (BODIPY) chromophores are described. Specifically, we have prepared dipyrrin complexes of dichlorogallate (GADIPY) or phenylphosphenium (PHODIPY) units. Whereas cationic PHODIPY is labile, decomposing to a phosphine over time, GADIPY is readily prepared in good yield as a crystalline solid having moderate air- and water-stability. Crystallographically characterized GADIPY displays intense green photoluminescence (λem = 505 nm, Φem = 0.91 in toluene). These inaugural heavier main group element analogues of BODIPY offer a glimpse into the potential for elaboration to a panoply of chromophores with diverse photophysical properties.

Single Layer Graphene for Estimation of Axial Spatial Resolution in Confocal Raman Microscopy Depth Profiling.

Single layer graphene (SLG), with its angstrom-scale thickness and strong Raman scattering cross section, was adapted for measurement of the axial ( Z-direction) probe beam profile in confocal Raman microscopy depth-profiling experiments. SLG adsorbed to a glass microscope coverslip (SLG/SiO2) served as a platform for the estimation of axial spatial resolution. Profiles were measured by stepping the confocal probe volume through the SLG/SiO2 interface while measuring Raman scattering from the sample. Using a high numerical aperture (1.4 NA) oil immersion objective, axial profiles were derived from the graphene 2D vibrational mode and fit to a Lorentzian instrument response function (IRF). Subsequently, the Z-direction spatial resolution in depth-profiling studies of polymer interfaces was estimated through convolution of the Lorentzian IRF with a step function representing the ideal junction separating the phases of interest. In the study of a bipolar polymer membrane, confocal Raman depth profiles of the AEM/CEM (anion exchange membrane/cation exchange membrane) interface show that the transition region is broader than the limiting response and are consistent with roughness at the boundary on the order of a few micrometers. Using ClO4- as a Raman active mobile ion probe, application of self-modeling curve resolution (SMCR) to spectral data sets within a profile showed ClO4- ions track the spatial distribution of the AEM phase. Finally, in measurements on a liquid-solid interface formed between 1-octanol and a polydimethylsiloxane (PDMS) membrane, the IRF derived from fitting the experimental profile was slightly narrower than those obtained from profiling SLG, indicating the potential to use polymer-liquid interfaces formed from widely available materials and reagents for estimation of axial spatial resolution in confocal Raman depth-profiling.

Thermal processing as a means to prepare durable, submicron thickness ionomer films for study by transmission infrared spectroscopy.

A high temperature solution processing method was adapted to prepare durable, freestanding, submicrometer thickness films for transmission infrared spectroscopy studies of ionomer membrane. The materials retain structural integrity following cleaning and ion-exchange steps in boiling solutions, similar to a commercial fuel cell membrane. Unlike commercial membrane, which typically has thicknesses of >25 µm, the structural properties of the submicrometer thickness materials can be probed in mid-infrared spectral measurements with the use of transmission sampling. Relative to the infrared attenuated total reflection (ATR) technique, transmission measurements can sample ionomer membrane materials more uniformly and suffer less distortion from optical effects. Spectra are reported for thermally processed Nafion and related perfluoroalkyl ionomer materials containing phosphonate and phosphinate moieties substituted for the sulfonate end group on the side chain. Band assignments for complex or unexpected features are aided by density functional theory (DFT) calculations.

Mesoporous carbon/zirconia composites: a potential route to chemically functionalized electrically-conductive mesoporous materials.

Mesoporous nanocomposite materials in which nanoscale zirconia (ZrO(2)) particles are embedded in the carbon skeleton of a templated mesoporous carbon matrix were prepared, and the embedded zirconia sites were used to accomplish chemical functionalization of the interior surfaces of mesopores. These nanocomposite materials offer a unique combination of high porosity (e.g., ∼84% void space), electrical conductivity, and surface tailorability. The ZrO(2)/carbon nanocomposites were characterized by thermogravimetric analysis, nitrogen-adsorption porosimetry, helium pychnometry, powder X-ray diffraction, Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. Comparison was made with templated mesoporous carbon samples prepared without addition of ZrO(2). Treatment of the nanocomposites with phenylphosphonic acid was undertaken and shown to result in robust binding of the phosphonic acid to the surface of ZrO(2) particles. Incorporation of nanoscale ZrO(2) surfaces in the mesoporous composite skeleton offers unique promise as a means for anchoring organophosphonates inside of pores through formation of robust covalent Zr-O-P bonds.

High-Resolution Ion-Flux Imaging of Proton Transport through Graphene|Nafion Membranes.

In 2014, it was reported that protons can traverse between aqueous phases separated by nominally pristine monolayer graphene and hexagonal boron nitride (h-BN) films (membranes) under ambient conditions. This intrinsic proton conductivity of the one-atom-thick crystals, with proposed through-plane conduction, challenged the notion that graphene is impermeable to atoms, ions, and molecules. More recent evidence points to a defect-facilitated transport mechanism, analogous to transport through conventional ion-selective membranes based on graphene and h-BN. Herein, local ion-flux imaging is performed on chemical vapor deposition (CVD) graphene|Nafion membranes using an "electrochemical ion (proton) pump cell" mode of scanning electrochemical cell microscopy (SECCM). Targeting regions that are free from visible macroscopic defects (e.g., cracks, holes, etc.) and assessing hundreds to thousands of different sites across the graphene surfaces in a typical experiment, we find that most of the CVD graphene|Nafion membrane is impermeable to proton transport, with transmission typically occurring at ≈20-60 localized sites across a ≈0.003 mm2 area of the membrane (>5000 measurements total). When localized proton transport occurs, it can be a highly dynamic process, with additional transmission sites "opening" and a small number of sites "closing" under an applied electric field on the seconds time scale. Applying a simple equivalent circuit model of ion transport through a cylindrical nanopore, the local transmission sites are estimated to possess dimensions (radii) on the (sub)nanometer scale, implying that rare atomic defects are responsible for proton conductance. Overall, this work reinforces SECCM as a premier tool for the structure-property mapping of microscopically complex (electro)materials, with the local ion-flux mapping configuration introduced herein being widely applicable for functional membrane characterization and beyond, for example in diagnosing the failure mechanisms of protective surface coatings.

High Performance of Anion Exchange Blend Membranes Based on Novel Phosphonium Cation Polymers for All-Vanadium Redox Flow Battery Applications.

The deployment of alkaline anion exchange membranes (AEMs) in flow battery applications has the advantage of a low cationic species crossover rate. However, the alkaline stability conjugated to the low conductivity of hydroxide ions of anion exchange membranes (AEMs) still represents a major drawback for the large deployment of such technology. In this study, three types of tetraarylpolyphosphonium (pTAP)-based copolymers (namely, CP1, CP2, and CP3) are synthesized and blended with chitosan and polyvinylidene fluoride (PVDF) for the fabrication of AEMs. Chitosan, a green biopolymer, was employed as a blend to enhance the water uptake of the base ionomer matrix. It is proposed that the abundancy of hydroxyl groups in chitosan improves considerably the ionic conductivity, water transport, and ion selectivity of the membrane, together with facilitating the dispersion of the chitosan in the pTAP copolymer matrix. The purpose of blending PVDF is instead to provide stable mechanical strength to the composite blend. The chemical, mechanical, and thermal stabilities of the three fabricated composite-blend membranes (i.e., CM1, CM2, and CM3) were characterized. All the membranes exhibited a high water retaining capacity of up to 36.26% (recorded for CM2) along with a hydroxyl ion conductivity of 17.39 mS cm-1. Due to the strong interactions between pTAP copolymers, chitosan, and PVDF polymers (confirmed also by Fourier transform infrared spectroscopy), the studied anion exchange membranes are able to retain up to 97% of the original OH conductivity after 1 M KOH treatment at room temperature for 100 h. The three membranes, namely, CM1, CM2, and CM3, have vanadium ion permeabilities measured at 20 °C of 1.775 × 10-8, 1.718 × 10-8, and 1.648 × 10-8 cm2/s, respectively, which are lower than that for the commercially available Nafion. The good stability and remarkable cell performance of the composite-blend membranes reported here make them definitely excellent candidates for the future generation of vanadium redox flow batteries.

Investigating the suitability of poly tetraarylphosphonium based anion exchange membranes for electrochemical applications.

Anion exchange membranes (AEMs) are becoming increasingly common in electrochemical energy conversion and storage systems around the world (EES). Proton-/cation-exchange membranes (which conduct positive charged ions such as H+ or Na+) have historically been used in many devices such as fuel cells, electrolysers, and redox flow batteries. High capital costs and the use of noble metal catalysts are two of the current major disadvantages of polymer electrolyte membrane (PEM)-based systems. AEMs may be able to overcome the limitations of conventional PEMs. As a result, polymers with anion exchange properties have recently attracted a lot of attention due to their significant benefits in terms of transitioning from a highly acidic to an alkaline environment, high kinetics for oxygen reduction and fuel oxidation in an alkaline environment, and lower cost due to the use of non-precious metals. The aim of this research was to learn more about the development of a new AEM based on poly tetraarylphosphonium ionomers (pTAP), which has high ionic conductivity, alkaline stability, thermal stability, and good mechanical properties, making it a more cost-effective and stable alternative to conventional and commercial AEMs. A simple solution casting method was used to build novel anion exchange composite membranes with controlled thicknesses using the synthesized pTAP with polysulfone (PS). To ensure their suitability for use as an electrolyte in alkaline electrochemical systems, the composite membranes were characterized using FTIR, XRD, water uptake, ionic conductivity, and alkaline stability. At 40 °C, the PS/pTAP 40/60 percent membrane had a maximum ionic conductivity of 4.2 mS/cm. The thermal and mechanical stability of the composite membranes were also examined, with no substantial weight loss observed up to 150 °C. These findings pave the way for these membranes to be used in a wide variety of electrochemical applications.

Perfluoroalkyl phosphonic and phosphinic acids as proton conductors for anhydrous proton-exchange membranes.

A study of proton-transport rates and mechanisms under anhydrous conditions using a series of acid model compounds, analogous to comb-branch perfluorinated ionomers functionalized with phosphonic, phosphinic, sulfonic, and carboxylic acid protogenic groups, is reported. Model compounds are characterized with respect to proton conductivity, viscosity, proton, and anion (conjugate base) self-diffusion coefficients, and Hammett acidity. The highest conductivities, and also the highest viscosities, are observed for the phosphonic and phosphinic acid model compounds. Arrhenius analysis of conductivity and viscosity for these two acids reveals much lower activation energies for ion transport than for viscous flow. Additionally, the proton self-diffusion coefficients are much higher than the conjugate-base self-diffusion coefficients for these two acids. Taken together, these data suggest that anhydrous proton transport in the phosphonic and phosphinic acid model compounds occurs primarily by a structure-diffusion, hopping-based mechanism rather than a vehicle mechanism. Further analysis of ionic conductivity and ion self-diffusion rates by using the Nernst-Einstein equation reveals that the phosphonic and phosphinic acid model compounds are relatively highly dissociated even under anhydrous conditions. In contrast, sulfonic and carboxylic acid-based systems exhibit relatively low degrees of dissociation under anhydrous conditions. These findings suggest that fluoroalkyl phosphonic and phosphinic acids are good candidates for further development as anhydrous, high-temperature proton conductors.

Infrared spectroscopy of bis[(perfluoroalkyl)sulfonyl] imide ionomer membrane materials.

Structural properties of the proton-exchanged forms of bis[(perfluoroalkyl)sulfonyl] imide (PFSI) ionomer materials were investigated. The hydration and dehydration of samples prepared as thin films and freestanding membrane were probed by applying transmission infrared spectroscopy. Spectral bands were assigned and effects of water incorporation into membrane pores and channels were understood by drawing upon results from related measurements performed on the structurally similar, perfluorosulfonic acid ionomer, Nafion. Both PFSI and Nafion membrane materials display a prominent infrared absorbance band near 1060 cm(-1) that arises from a vibrational mode of the ionizable group present on the side chains that extend from the poly(tetrafluoroethylene) backbone on the polymers. The mode can be traced to symmetric stretching of the -SO(3)(-) (sulfonate) group in Nafion and to antisymmetric S-N-S stretching within the sulfonyl imide end group (-SO(2)(N(-))SO(2)CF(3)) in the PFSI materials. For Nafion samples, the position and width of the band near 1060 cm(-1) are strongly sensitive to membrane hydration, whereas the band position and shape change only slightly during hydration and dehydration of PFSI materials. The possibility for greater charge delocalization over the sulfonyl imide moiety and shielding of hydrophilic species by the terminal -CF(3) group are suggested to explain the differences. These effects also likely influence the stretching modes of the side chain C-O-C groups. A pair of bands, sensitive to hydration and traceable to different C-O-C groups in a side chain, is present in the 970-990 cm(-1) region of Nafion. However, the two features are not well resolved and are less sensitive to hydration in spectra of PFSI samples. The most intense ionomer spectral bands arise from modes involving C-F stretching motion and appear between 1150 and 1250 cm(-1). Toward the high energy side of the envelope, there is substantial overlap with features of sulfonate group antisymmetric SO stretching modes in Nafion, but SO stretching modes of the sulfonyl imide moiety are higher in energy and better resolved in spectra of the PFSIs. During water uptake from a dry state into PFSI materials, a progression of features characteristic of solvated H(3)O(+) species appears across the water O-H stretching (2800-3800 cm(-1)) and H-O-H bending (1500-2000 cm(-1)) regions, similar to responses observed for water inside proton-exchanged Nafion.

A Versatile Carbon Nanotube-Based Scalable Approach for Improving Interfaces in Li-Ion Battery Electrodes.

Resistive interfaces within the electrodes limit the energy and power densities of a battery, for example, a Li-ion battery (LIB). Typically, active materials are mixed with conductive additives in organic solvents to form a slurry, which is then coated on current collectors (e.g., bare or carbon-coated Al foils) to reduce the inherent resistance of the active material. Although many approaches using nanomaterials to either replace Al foils or improve conductivity within the active materials have been previously demonstrated, the resistance at the current collector active material interface (CCAMI), a key factor for enhancing the energy and power densities, remains unaddressed. We show that carbon nanotubes (CNTs), either directly grown or spray-coated on Al foils, are highly effective in reducing the CCAMI resistance of traditional LIB cathode materials (LiFePO4 or LFP and LiNi0.33Co0.33Mn0.33O2 or NMC). Moreover, the CNT coatings displace the need for currently used toxic organic solvents (e.g., N-methyl-2-pyrrolidone) by providing capillary channels, which improve the wetting of aqueous dispersions containing active materials. The vertically aligned CNT-coated electrodes exhibited energy densities as high as (1) ∼500 W h kg-1 at ∼170 W kg-1 for LFP and (2) ∼760 W h kg-1 at ∼570 W kg-1 for NMC. The LIBs with CCAMI-engineered electrodes withstood discharge rates as high as 600 mA g-1 for 500 cycles in the case of LFP, where commercial electrodes failed. The CNT-based CCAMI engineering approach is versatile with wide applicability to improve the performance of even textured active materials for both cathodes and anodes.

Vibrational Spectroscopy for the Determination of Ionizable Group Content in Ionomer Materials.

An approach based on vibrational spectral measurements is described for determining the ionizable group content of ion conducting polymer membrane materials. Aimed at supporting the assessment of membrane stability and wear characteristics, performance is evaluated for attenuated total reflection Fourier transform infrared (ATR FT-IR) spectroscopy, confocal Raman microscopy, and ATR FT-IR microscopy using perfluorinated ionomer membrane standards. One set of ionomer standards contained a sulfonic acid ionizable group and the other a sulfonyl imide group. The average number of backbone tetrafluoroethylene (TFE) units separating the ionizable-group containing side chains was in the range of 7.2-2.1 (sulfonic acid set) and 10.5-4.6 (sulfonyl imide set). A poly(tetrafluoroethylene) (PTFE) sample was included as a blank, representing the limit of zero ionizable group (and maximum TFE) content. Calibration relationships were derived from area-normalized vibrational spectra. For all three methods, calibration models applied to independent spectral measurements of samples predicted the ratio of backbone TFE groups to ionizable groups in the repeat unit ( m) with a standard error of ≤ ±0.3. The confocal Raman and ATR FT-IR microscopy techniques achieved ideal blank responses and the lowest prediction errors, down to m ± 0.1 at the 90% confidence level. With its relative simplicity, low sample size requirements, and potential for quantitative micron-scale spatial mapping of the ionizable group content within a membrane, the approach has application to advancing materials development, including exploratory synthesis, durability and wear assessment, and in situ studies of membrane process.

Transport properties of solid polymer electrolytes prepared from oligomeric fluorosulfonimide lithium salts dissolved in high molecular weight poly(ethylene oxide).

Transport properties such as ionic conductivity, lithium transference number, and apparent salt diffusion coefficient are reported for solid polymer electrolytes (SPEs) prepared using several oligomeric bis[(perfluoroalkyl)sulfonyl]imide (fluorosulfonimide) lithium salts dissolved in high molecular weight poly(ethylene oxide) (PEO). The salt series consists of polyanions in which two discrete fluorosulfonimide anions are linked together by [(perfluorobutylene)disulfonyl]imide linker chains. The restricted diffusion technique was used to measure the apparent salt diffusion coefficients in SPEs, and cationic transference numbers were determined using both potentiostatic polarization and electrochemical impedance spectroscopy methods. A general trend of diminished salt diffusion coefficient with increasing anion size was observed and is opposite to the trend observed in ionic conductivity. This unexpected finding is rationalized in terms of the cumulative effects of charge carrier concentration, anion mobility, ion pairing, host plasticization by the anions, and salt phase segregation on the conductivity.

Li+ transport in lithium sulfonylimide-oligo(ethylene oxide) ionic liquids and oligo(ethylene oxide) doped with LiTFSI.

The Li+ environment and transport in an ionic liquid (IL) comprised of Li+ and an anion of bis(trifluoromethanesulfonyl)imide anion (TFSI-) tethered to oligoethylene oxide (EO) (EO(12)TFSI-/Li+) were determined and compared to those in a binary solution of the oligoethylene oxide with LiTFSI salt (EO(12)/LiTFSI) by using molecular dynamics (MD) simulations and AC conductivity measurements. The latter revealed that the AC conductivity is 1 to 2 orders of magnitude less in the IL compared to the oligoether/salt binary electrolyte with greater differences being observed at lower temperatures. The conductivity of these electrolytes was accurately predicted by MD simulations, which were used in conjunction with a microscopic model to determine mechanisms of Li+ transport. It was discerned that structure-diffusion of the Li+ cation in the binary electrolyte (EO(12)/LiTFSI-) was similar to that in EO(12)TFSI-/Li+ IL at high temperature (>363 K), thus, one can estimate conductivity of IL at this temperature range if one knows the structure-diffusion of Li+ in the binary electrolyte. However, the rate of structure-diffusion of Li+ in IL was found to slow more dramatically with decreasing temperature than in the binary electrolyte. Lithium motion together with EO(12) solvent accounted for 90% of Li+ transport in EO(12)/LiTFSI-, while the Li+ motion together with the EO(12)TFSI- anion contributed approximately half to the total Li+ transport but did not contribute to the charge transport in IL.

Nonvolatile optically-erased colloidal memristors.

A nonconjugated methacrylate terpolymer containing carbazole moieties (electron donors), 1,3,4-oxadiazole moieties (electron acceptors), and Coumarin-6 in the pendant groups was synthesized via free radical copolymerization of methacrylate monomers containing the respective functional groups. The terpolymer was formed into 57 nm particles through a mini-emulsion route. For a thin 100 nm film of the fused particles sandwiched between an indium-tin oxide (ITO) electrode and an Al electrode, the structure behaved as a nonvolatile flash (rewritable) memory with accessible electronic states that could be written, read, and optically erased. The device exhibited a turn-on voltage of ca. -4.5 VDC and a 10(6) current ratio. A device in the ON high conductance state could be reverted to the OFF state with a short exposure to a 360 nm light source. The development of semiconducting colloidal inks that can be converted into electroactive devices through a continuous processing method is a critical step in the widespread adoption of these 2D manufacturing technologies for printed electronics.

Electrochemical behavior of platinum nanoparticles on a carbon xerogel support modified with a [(trifluoromethyl)-benzenesulfonyl]imide electrolyte.

A monoprotic [(trifluoromethyl)benzenesulfonyl]imide (SI) superacid electrolyte was used to covalently modify a mesoporous carbon xerogel (CX) support via reaction of the corresponding trifluoromethyl aryl sulfonimide diazonium zwitterion with the carbon surface. Electrolyte attachment was demonstrated by elemental analysis, acid-base titration, and thermogravimetric analysis. The ion-exchange capacity of the fluoroalkyl-aryl-sulfonimide-grafted carbon xerogel (SI-CX) was ∼0.18 mequiv g(-1), as indicated by acid-base titration. Platinum nanoparticles were deposited onto the SI-grafted carbon xerogel samples by the impregnation and reduction method, and these materials were employed to fabricate polyelectrolyte membrane fuel-cell (PEMFC) electrodes by the decal transfer method. The SI-grafted carbon-xerogel-supported platinum (Pt/SI-CX) was characterized by X-ray diffraction and transmission electron microscopy to determine platinum nanoparticle size and distribution, and the findings are compared with CX-supported platinum catalyst without the grafted SI electrolyte (Pt/CX). Platinum nanoparticle sizes are consistently larger on Pt/SI-CX than on Pt/CX. The electrochemically active surface area (ESA) of platinum catalyst on the Pt/SI-CX and Pt/CX samples was measured with ex situ cyclic voltammetry (CV) using both hydrogen adsorption/desorption and carbon monoxide stripping methods and by in situ CV within membrane electrode assemblies (MEAs). The ESA values for Pt/SI-CX are consistently lower than those for Pt/CX. Some possible reasons for the behavior of samples with and without grafted SI layers and implications for the possible use of SI-grafted carbon layers in PEMFC devices are discussed.

The effect of low-molecular-weight poly(ethylene glycol) (PEG) plasticizers on the transport properties of lithium fluorosulfonimide ionic melt electrolytes.

The influence of low-molecular-weight poly(ethylene glycol) (PEG, Mw ≈ 550 Da) plasticizers on the rheology and ion-transport properties of fluorosulfonimide-based polyether ionic melt (IM) electrolytes has been investigated experimentally and via molecular dynamics (MD) simulations. Addition of PEG plasticizer to samples of IM electrolytes caused a decrease in electrolyte viscosity coupled to an increase in ionic conductivity. MD simulations revealed that addition of plasticizer increased self-diffusion coefficients for both cations and anions with the plasticizer being the fastest diffusing species. Application of a VTF model to fit variable-temperature conductivity and fluidity data shows that plasticization decreases the apparent activation energy (Ea) and pre-exponential factor A for ion transport and also for viscous flow. Increased ionic conductivity with plasticization is thought to reflect a combination of factors including lower viscosity and faster polyether chain segmental dynamics in the electrolyte, coupled with a change in the ion transport mechanism to favor ion solvation and transport by polyethers derived from the plasticizer. Current interrupt experiments with Li/electrolyte/Li cells revealed evidence for salt concentration polarization in electrolytes containing large amounts of plasticizer but not in electrolytes without added plasticizer.

Grafting of chain-end-functionalized perfluorocyclobutyl (PFCB) aryl ether ionomers onto mesoporous carbon supports.

Water-soluble perfluorocyclobutyl (PFCB) aryl ether ionomers bearing sulfonic acid groups in the main chain and phosphonic acid end groups were prepared and used to modify the surfaces of mesoporous carbon materials containing dispersed zirconia nanoparticles. Ionomer surface grafting occurred via phosphonate bonding onto the zirconia particle surfaces.

Evaluation of non-specific binding suppression schemes for neutravidin and alkaline phosphatase at the surface of reticulated vitreous carbon electrodes.

Non-specific binding (NSB) of high-molecular-weight proteins onto electrode surfaces can complicate the application of electroanalytical techniques to clinical and environmental research, particularly in biosensor applications. We present herein various strategies to modify the surface of reticulated vitreous carbon (RVC) electrodes to suppress non-specific binding of biomolecules onto its surface. Non-specific binding and specific binding (SB) of two enzyme conjugates, neutravidin-alkaline phosphatase (NA-ALP) and biotinylated alkaline phosphatase (B-ALP), and also neutravidin itself, were studied using hydroquinone diphosphate (HQDP) as an enzyme substrate for ALP inside the pores of RVC electrodes that had been subjected to various modification schemes. The extent of NSB and SB of these biomolecules inside RVC pores was assessed by measuring the initial rate of generation of an electroactive product, hydroquinone (HQ), of the enzyme-catalyzed reaction, using linear scan voltammetry (LSV) for HQ detection. Electrodes functionalized with phenylacetic acid and poly(ethylene glycol) (PEG) showed low NSB and high SB (when biotin capture ligands were included in the modification scheme) in comparison with unmodified electrodes and RVC electrodes modified in other ways. A simple sandwich bioassay for neutravidin was performed on the RVC electrode with the lowest NSB. A concentration detection limit of 52+/-2 ng mL(-1) and an absolute detection limit of 5.2+/-0.2 ng were achieved for neutravidin when this assay was performed using a 100 microL sample size.

Effect of perfluoroalkyl chain length on proton conduction in fluoroalkylated phosphonic, phosphinic, and sulfonic acids.

The effects of increasing perfluoroalkyl chain length on the molecular properties of viscosity, diffusivity, and ionic conductivity of a series of acid model compounds analogous to comb-branch perfluorinated ionomers functionalized with phosphonic, phosphinic, and sulfonic protogenic groups are reported. Anhydrous proton transport by a Grotthuss-like hopping mechanism was observed to occur efficiently in phosphorus-based fluoroalkylated model acids but only when there is a relatively low perfluoroalkyl content. The decrease in degree of dissociation of the protogenic groups follows the order phosphonic > phosphinic > sulfonic, and the degree of dissociation and the magnitude of ion-ion correlations are approximately independent of chain length.