Polythiophene Doping of the Cu-Based Metal-Organic Framework (MOF) HKUST-1 Using Innate MOF-Initiated Oxidative Polymerization.

The copper-based metal-organic framework (MOF) HKUST-1 adsorbs organic molecules into its pores. When loaded with electron-rich oligothiophenes, the resulting system reacts under heat to initiate oxidative polymerization without the use of any other oxidant or catalyst. This reaction is not observed in the non-redox-active MOF MIL-100(Al). We have characterized the composites by optical and nanoscale microscopy, vibrational and UV-vis spectroscopy, X-ray photoelectron spectroscopy, N2 sorption analysis, and thermogravimetric analysis/residual gas analysis. Unsubstituted oligothiophenes polymerize within MOF pores, while 3,4-ethylenedioxythiophene forms a coating on the MOF surface. MOF composites with conjugated polymer dopants trapped inside their pores undergo profound shifts in the composite electronic structure. Reasoning from time-dependent density functional theory calculations of an HKUST-1 model system bound to monomers, we rationalize the observed reactivity and propose an initiation mechanism based on a ligand-to-metal charge-transfer state.

Diazonium-functionalized thin films from the spontaneous reaction of p-phenylenebis(diazonium) salts.

Salts of the diazonium coupling agent p-phenylenebis(diazonium) form diazonium-terminated conjugated thin films on a variety of conductive and nonconductive surfaces by spontaneous reaction of the coupling agent with the surface. The resulting diazonium-bearing surface can be reacted with various organic and inorganic nucleophiles to form a functionalized surface. These surfaces have been characterized with voltammetry, XPS, infrared and Raman spectroscopy, and atomic force microscopy. Substrates that can be conveniently and quickly modified with this process include ordinary glass, gold, and an intact, fully assembled commercial screen-printed carbon electrode. The scope and convenience of this process make it promising for practical surface modification.

Stern potential and Debye length measurements in dilute ionic solutions with electrostatic force microscopy.

We demonstrate the ability to measure Stern potential and Debye length in dilute ionic solution with atomic force microscopy. We develop an analytic expression for the second harmonic force component of the capacitive force in an ionic solution from the linearized Poisson-Boltzmann equation. This allows us to calibrate the AFM tip potential and, further, obtain the Stern potential of sample surfaces. In addition, the measured capacitive force is independent of van der Waals and double layer forces, thus providing a more accurate measure of Debye length.

Dielectric constants by multifrequency non-contact atomic force microscopy.

We present a method to obtain capacitive forces and dielectric constants of ultra-thin films on metallic substrates using multifrequency non-contact atomic force microscopy with amplitude feedback in air. Capacitive forces are measured via cantilever oscillations induced at the second bending mode and dielectric constants are calculated by fitting an analytic expression for the capacitance (Casuso et al 2007 Appl. Phys. Lett. 91 063111) to the experimental data. Dielectric constants for self-assembled monolayers of thiol molecules on gold (2.0±0.1) and sputtered SiO2 (3.6±0.07) were obtained under dry conditions, in good agreement with previous measurements. The high Q-factor of the second bending mode of the cantilever increases the accuracy of the capacitive measurements while the low applied potentials minimize the likelihood of variation of the dielectric constants at high field strength and of damage from dielectric breakdown of air.

Dependence of surface-enhanced infrared absorption (SEIRA) enhancement and spectral quality on the choice of underlying substrate: a closer look at silver (Ag) films prepared by physical vapor deposition (PVD).

Silver (Ag) films of varying thickness were simultaneously deposited using physical vapor deposition (PVD) onto six infrared (IR) substrates (BaF(2), CaF(2), Ge, AMTIR, KRS-5, and ZnSe) in order to correlate the morphology of the deposited film with optimal SEIRA response and spectral band symmetry and quality. Significant differences were observed in the surface morphology of the deposited silver films, the degree of enhancement provided, and the spectral appearance of para-nitrobenzoic acid (PNBA) cast films for each silver-coated substrate. These differences were attributed to each substrate's chemical properties, which dictate the morphology of the Ag film and ultimately determine the spectral appearance of the adsorbed analyte and the magnitude of SEIRA enhancement. Routine SEIRA enhancement factors (EFs) for all substrates were between 5 and 150. For single-step Ag depositions, the following ranking identifies the greatest SEIRA enhancement factor and the maximum absorption of the 1345 cm(-1) spectral marker of PNBA at the optimal silver thickness for each substrate: BaF(2) (EF = 85 ± 19, 0.059 A, 10 nm Ag) > CaF(2) (EF = 75 ± 30, 0.052 A, 10 nm Ag) > Ge (EF = 45 ± 8, 0.019 A, 5 nm Ag) > AMTIR (EF = 38 ± 8, 0.024 A, 15 nm Ag) > KRS-5 (EF = 24 ± 1, 0.015 A, 12 nm Ag) > ZnSe (EF = 9 ± 5, 0.008 A, 8 nm Ag). A two-step deposition provides 59% larger EFs than single-step depositions of Ag on CaF(2). A maximum EF of 147 was calculated for a cast film of PNBA (surface coverage = 341 ng/cm(2)) on a 10 nm two-step Ag film on CaF(2) (0.102 A, 1345 cm(-1) symmetric NO(2) stretching band). The morphology of the two-step Ag film has smaller particles and greater particle density than the single-step Ag film.

Effect of electron mediators on current generation and fermentation in a microbial fuel cell.

Effects of select electron mediators [9,10-anthraquinone-2,6-disulfonic acid disodium salt (AQDS), safranine O, resazurin, methylene blue, and humic acids] on metabolic end-products and current production from cellulose digestion by Clostridium cellulolyticum in microbial fuel cells (MFCs) were studied using capillary electrophoresis and traditional electrochemical techniques. Addition of the mediator resazurin greatly enhanced current production but did not appear to alter the examined fermentation end-products compared to MFCs with no mediator. Assays for lactate, acetate, and ethanol indicate that the presence of safranine O, methylene blue, and humic acids alters metabolite production in the MFC: safranine O decreased the examined metabolites, methylene blue increased lactate formation, and humic acids increased the examined metabolites. Mediator standard redox potentials (E (0)) reported in the literature do not coincide with redox potentials in MFCs due presumably to the electrolytic complexity of media that supports bacterial survival and growth. Current production in MFCs: (1) can be effected by the mediator redox potential while in the media, which may be significantly shifted from E (0), and (2) depended on the ability of the mediator to access the bacterial electron source, which may be cytoplasmic. In addition, some electron mediators had significant effects on metabolic end-products and therefore the metabolism of the organism itself.

Mediating electron transfer from bacteria to a gold electrode via a self-assembled monolayer.

Numerous bacterial genera are known to respire anaerobically using macroscopic electrodes as electron acceptors. Typically, inexpensive graphite electrodes, which are readily colonized, are used to monitor electrogenic bacterial metabolism for microbial fuel cell and bioelectronics studies. We compare current production by electrogenic bacteria on gold electrodes coated with various alkanethiol self-assembled monolayers to current production on glassy carbon electrodes. Current production is correlated to chain length and headgroup of the monolayer molecules as expected. Relative to graphite, the coated gold electrodes achieve more reproducible experimental conditions and certain headgroups enhance electronic coupling to the bacteria.