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We report a highly controlled technique for the synthesis of polymer films atop a substrate by combining spin coating with ring-opening metathesis polymerization (ROMP), herein termed spin coating ROMP (scROMP). The scROMP approach combines polymer synthesis and deposition into one process, fabricating films of up to 36 cm 2 in under 3 min with orders-of-magnitude reduction in solvent usage. This method can convert numerous norbornene-type molecules into homopolymers and random copolymers as uniform films on both porous and nonporous substrates. Film thickness can be varied from a few hundred nanometers to a few tens of micrometers based on spin speed and monomer concentration. The resulting polymers possess high M W (>100 kDa) and low polydispersity (PDI) (<1.2) values that are similar to ROMP polymers made in solution. We also devise a model to investigate the balance between convective monomer spin-off and polymer growth from the surface, which allows the determination of critical kinetic parameters for scROMP. Finally, translation of scROMP to porous supports enables the synthesis of thin film composite membranes that demonstrate the ability to dehydrate ethanol by pervaporation.

Photosystem I (PSI) is an intrinsically photoactive multi-subunit protein that is found in higher order photosynthetic organisms. PSI is a promising candidate for renewable biohybrid energy applications due to its abundance in nature and its high quantum yield. To utilize PSI's light-responsive properties and to overcome its innate electrically insulating nature, the protein can be paired with a biologically compatible conducting polymer that carries charge at appropriate energy levels, allowing excited PSI electrons to travel within a composite network upon light excitation. Here, a substituted aniline, 4-methoxy-aniline ( para -anisidine), is chemically oxidized to synthesize poly( p -anisidine) (PPA) and is interfaced with PSI for the fabrication of PSI-PPA composite films by drop casting. The resulting PPA polymer is characterized in terms of its structure, composition, thermal decomposition, spectroscopic response, morphology, and conductivity. Combining PPA with PSI yields composite films that exhibit photocurrent densities on the order of several μA cm -2 when tested with appropriate mediators in a 3-electrode setup. The composite films also display increased photocurrent output when compared to single-component films of the protein or PPA alone to reveal a synergistic combination of the film components. Tuning film thickness and PSI loading within the PSI-PPA films yields optimal photocurrents for the described system, with ∼2 wt% PSI and intermediate film thicknesses generating the highest photocurrents. More broadly, dilute PSI concentrations show significant importance in achieving high photocurrents in PSI-polymer films., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The combination of conducting polymers with electro- and photoactive proteins into thin films holds promise for advanced energy conversion materials and devices. The emerging field of protein electronics requires conductive soft materials in a composite with electrically insulating proteins. The electropolymerization of pyrrole through voids in a drop-casted photosystem I (PSI) multilayer film enables the straightforward fabrication of photoactive and conductive biohybrid films. The rate of polypyrrole (PPy) growth is reduced by the presence of the PSI film but is insensitive to its thickness, suggesting that rapid diffusion of pyrrole through the voids within the PSI film enables initiation at vacant areas on the gold surface. The base thickness of the composite tends to increase with time, as PPy chains propagate through and beyond the PSI film, coalescing to exhibit a tubule-like morphology as observed by scanning electron microscopy. Increasing amounts of PPy greatly increase the capacitance of the composite films in a manner almost identical to that of pure PPy films grown from unmodified gold, consistent with a high polymer/aqueous interfacial area and a conductive composite film. While PPy is not photoactive here, all composite films, including those with large amounts of PPy, exhibit photocurrents when irradiated by white light in the presence of redox mediator species. Optimization of the Py electropolymerization time is necessary, as increasing amounts of PPy lead to decreased photocurrent density due to a combination of light absorbance by the polymer and reduced accessibility of redox species to active PSI sites., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

One of the main barriers to making efficient Photosystem I-based biohybrid solar cells is the need for an electrochemical pathway to facilitate electron transfer between the P 700 reaction center of Photosystem I and an electrode. To this end, nature provides inspiration in the form of cytochrome c 6 , a natural electron donor to the P 700 site. Its natural ability to access the P 700 binding pocket and reduce the reaction center can be mimicked by employing cytochrome c, which has a similar protein structure and redox chemistry while also being compatible with a variety of electrode surfaces. Previous research has incorporated cytochrome c to improve the photocurrent generation of Photosystem I using time consuming and/or specialized electrode preparation. While those methods lead to high protein areal density, in this work we use the quick and facile vacuum-assisted drop-casting technique to construct a Photosystem I/cytochrome c photoactive composite film with micron-scale thickness. We demonstrate that this simple fabrication technique can result in high cytochrome c loading and improvement in cathodic photocurrent over a drop-casted Photosystem I film without cytochrome c. In addition, we analyze the behavior of the cytochrome c/Photosystem I system at varying applied potentials to show that the improvement in performance can be attributed to enhancement of the electron transfer rate to P 700 sites and therefore the PSI turnover rate within the composite film., (© 2022. The Author(s), under exclusive licence to Springer Nature B.V.)

We present a new route for obtaining surface-tethered polymer films containing pendant catechol functional groups via surface-initiated activators regenerated by electron-transfer atom-transfer radical polymerization (SI-ARGET ATRP) of glycidyl methacrylate (GMA) and post-polymerization modification of the resulting poly(glycidyl methacrylate) (pGMA) films with dopamine. This method enables a high degree of functionalization of pGMA films with catechol groups at a controlled level, depending on the duration of the post-polymerization modification reaction. The dopamine-pGMA films readily absorbs Al 3+ and Zn 2+ ions, as verified by quartz crystal microbalance with dissipation (QCM-D) under continuous flow conditions, and demonstrates a four-fold molar selectivity to Al 3+ over Zn 2+ . The ions desorb from the films upon rinsing with pure deionized (DI) water, which regenerates the catechol sites in the dopamine-pGMA film. Subsequent exposure to metal ions after rinsing steps yields reproducible levels of loading.

The design of electrode interfaces to achieve efficient electron transfer to biomolecules is important in many bioelectrochemical processes. Within the field of biohybrid solar energy conversion, constructing multilayered Photosystem I (PSI) protein films that maintain good electronic connection to an underlying electrode has been a major challenge. Previous shortcomings include low loadings, long deposition times, and poor connection between PSI and conducting polymers within composite films. Here, we show that PSI protein complexes can be deposited into monolayers within a 30 min timespan by leveraging the electrostatic interactions between the protein complex and the poly(3,4-ethylenedioxythiophene)-polystyrenesulfonate (PEDOT:PSS) polymer. Further, we follow a layer-by-layer (LBL) deposition procedure to produce up to 9-layer pairs of PSI and PEDOT:PSS with highly reproducible layer thicknesses as well as distinct changes in surface composition. When tested in an electrochemical cell employing ubiquinone-0 as a mediator, the photocurrent performance of the LBL films increased linearly by 83 ± 6 nA/cm 2 per PSI layer up to 6-layer pairs. The 6-layer pair samples yielded a photocurrent of 414 ± 13 nA/cm 2 , after which the achieved photocurrent diminished with additional layer pairs. The turnover number (TN) of the PSI-PEDOT:PSS LBL assemblies also greatly exceeds that of drop-casted PSI multilayer films, highlighting that the rate of electron collection is improved through the systematic deposition of the protein complexes and conducting polymer. The capability to deposit high loadings of PSI between PEDOT:PSS layers, while retaining connection to the underlying electrode, shows the value in using LBL assembly to produce PSI and PEDOT:PSS bioelectrodes for photoelectrochemical energy harvesting applications.

The photosystem I (PSI) protein complex is known to enhance bioelectrode performance for many liquid-based photoelectrochemical cells. A hydrogel as electrolyte media allows for simpler fabrication of more robust and practical solar cells in comparison to liquid-based devices. This paper reports a natural, gel-based dye-sensitized solar cell that integrates PSI to improve device efficiency. TiO 2 -coated FTO slides, dyed by blackberry anthocyanin, act as a photoanode, while a film of PSI deposited onto copper comprises the photocathode. Ascorbic acid (AscH) and 2,6-dichlorophenolindophenol (DCPIP) are the redox mediator couple inside an agarose hydrogel, enabling PSI to produce excess oxidized species near the cathode to improve device performance. A comparison of performance at low pH and neutral pH was performed to test the pH-dependent properties of the AscH/DCPIP couple. Devices at neutral pH performed better than those at lower pH. The PSI film enhanced photovoltage by 75 mV to a total photovoltage of 0.45 V per device and provided a mediator concentration-dependent photocurrent enhancement over non-PSI devices, reaching an instantaneous power conversion efficiency of 0.30% compared to 0.18% without PSI, a 1.67-fold increase. At steady state, power conversion efficiencies for devices with and without PSI were 0.042 and 0.028%, respectively.

Carbon dots (CDs) are a rapidly progressing class of nanomaterial which show promise towards applications in solar energy conversion due to their low toxicity, favorable electrochemical properties, and tunability. In recent years there have been a number of reported CD syntheses, both top-down and bottom-up methods, producing a diverse range of CDs with intrinsic properties dependent on the starting materials and utilized dopants. This work presents a citrate buffer-facilitated synthesis of nitrogen-doped carbon dots (NCD) and explores the impact of urea concentration on observed electrochemical and optical properties. Optical absorbance and quantum yield of NCDs were found to increase with the dopant concentrations present in the hydrothermal reaction mixture. Electrochemical analysis demonstrates that increased nitrogen content results in the shifting of carbon dot oxidation potentials without the need of post-synthesis surface modifications. Over the range of molar ratios of dopant-to-citrate tested, the oxidation potentials of NCDs shifted up to 150 mV towards more negative potentials. X-ray photoelectron spectroscopy confirms the addition of pyrrolic and pyridinic nitrogen at different levels in different batches of NCDs, which are likely the source of the observed changes., Competing Interests: The authors declare no conflict of interest., (This journal is © The Royal Society of Chemistry.)

We report the preparation of pH-responsive, ester/carboxylic acid random copolymer films via simple modification of poly(norbornene diacyl chloride) (pNBDAC), prepared via surface-initiated ring-opening metathesis polymerization, with mixtures of water and ethanol to form carboxylic acid and ethyl ester side groups. The pNBDAC film serves as a compositionally versatile platform to controllably obtain copolymers with multiple functionalities. In modifying the pNBDAC to form the copolymer film, ethanol exhibits a significantly higher reactivity with acyl chloride groups within the film than does water. The magnitude and range of the pH-responsive performance are highly dependent on the carboxylic acid content in the copolymer films, which demonstrates the effect of film hydrophilicity on the pH-responsive switching of ionic barrier properties. The resistance of the film against ion transfer can be decreased by a factor of 10 4 through pH change, demonstrating pH-induced switching from hydrophobic and insulating to swollen and ion-permeable films. The interactions of the copolymer films with water at different pH values were also explored. When the copolymer contains 34% carboxylic acids, a 4× greater film thickness is obtained in high pH solution than in low pH solution due to ionically driven water swelling. The reversibility of the pH-responsive performance of these copolymer films is high based on measurements using quartz crystal microbalance with dissipation (QCM-D).

We have designed and synthesized a series of new imidazole-based compounds structurally related to an antiprotozoal agent with nanomolar activity which we identified recently. The new analogues possess micromolar activities against Trypanosoma brucei rhodesiense and Leishmania donovani and nanomolar potency against Plasmodium falciparum. Most of the analogues displayed IC 50 within the low nanomolar range against Trypanosoma cruzi, with very high selectivity toward the parasite. Discussion of structure-activity relationships and in vitro biological data for the new compounds are provided against a number of different protozoa. The mechanism of action for the most potent derivatives (5i, 6a-c, and 8b) was assessed by a target-based assay using recombinant T. cruzi CYP51. Bioavailability and efficacy of selected hits were assessed in a T. cruzi mouse model, where 6a and 6b reduced parasitemia in animals >99% following intraperitoneal administration of 25 mg/kg/day dose for 4 consecutive days.

The photosynthetic protein complex, photosystem I (PSI), can be photoexcited with a quantum efficiency approaching unity and can be integrated into solar energy conversion devices as the photoactive electrode. The incorporation of PSI into conducting polymer frameworks allows for improved conductivity and orientational control in the photoactive layer. Polyviologens are a unique class of organic polycationic polymers that can rapidly accept electrons from a primary donor such as photoexcited PSI and subsequently can donate them to a secondary acceptor. Monomeric viologens, such as methyl viologen, have been widely used as diffusible mediators in wet PSI-based photoelectrochemical cells on the basis of their suitable redox potentials for accepting electrons. Polyviologens possess similar electronic properties to their monomers with the added advantage that they can shuttle electrons in the solid state. Depositing polyviologen directly onto a film of PSI protein results in significant photocurrent enhancement, which confirms its role as an electron-transport material. The polymer film not only improves the photocurrent by aiding the electron transfer but also helps preserve the protein film underneath. The composite polymer-PSI assembly enhances the charge-shuttling processes from individual protein molecules within the PSI multilayer, greatly reducing charge-transfer resistances. The resulting PSI-based solid-state platform demonstrates a much higher photocurrent than the corresponding photoelectrochemical cell built using a similar architecture.

This manuscript details a novel and simple approach to achieve surface-tethered co-poly(ionic liquid) (coPIL) films through the exchange of the resident anion of a poly(ionic liquid) (PIL) film with two or more anions. Initially, surface-tethered PIL films were prepared by the surface-initiated ring-opening metathesis polymerization of the ionic liquid monomer 3-[(bicyclo[2.2.1]hept-5-en-2-yl)methyl]-1,2-dimethylimidazol-3-ium hexafluorophosphate ([N 1 -dMIm][PF 6 ]) whose PF 6 - anion was easily interchanged with aqueous solutions containing a binary mixture of the PF 6 - anion, along with perchlorate (ClO 4 - ) or bis(fluorosulfonyl)imide (FSI - ) anions. The binary mole fraction of each anion in the film was determined from the infrared spectra of the coPIL films. The thermodynamically driven anion selectivity for exchange from the liquid phase into the coPIL films was determined to follow the order ClO 4 - < PF 6 - < FSI - . The aqueous wettability of p[N 1 -dMIm] coPIL films containing both the PF 6 - and ClO 4 - anions (p[N 1 -dMIm][PF 6 ][ClO 4 ]) was quantified by contact angle goniometry with the observation that the surface showed an enrichment in the ClO 4 - anion compared to the average binary anion mole fraction of ClO 4 - in the film ( y ClO 4 - ). The rate of ion transport through the p[N 1 -dMIm][PF 6 ][ClO 4 ] coPIL films, quantified by electrochemical impedance spectroscopy, linearly depends on the binary anion mole fraction of ClO 4 - in solution ( x ClO 4 - ), enabling continuous tunability by over three orders of magnitude for ion conductivity in the coPIL films., Competing Interests: The authors declare no competing financial interest.

We discovered a series of azole antifungal compounds as effective antiprotozoal agents. They displayed promising inhibitory activities within the micromolar-submicromolar range against P. falciparum, L. donovani, and T. b. rhodesiense. Moreover, most of such compounds showed excellent nanomolar IC 50 against T. cruzi, showing also very low cytotoxicity. Discussion of structure-activity relationships and biological data for these compounds are provided against the different parasites. To assess the mechanism of action against T. cruzi we proved that the most potent compounds (3b, 3j-l) inhibited the T. cruzi CYP51. Moreover, the most active derivative 3j dramatically reduced parasitemia in T. cruzi mouse model without acute toxicity., (Copyright © 2018 Elsevier Masson SAS. All rights reserved.)

Cytochrome P450 4B1 (4B1) functions in both xenobiotic and endobiotic metabolism. An ester linkage between Glu-310 in 4B1 and the 5-methyl group of heme facilitates preferential hydroxylation of terminal (ω) methyl groups of hydrocarbons (HCs) and fatty acids compared with ω-1 sites bearing weaker C-H bonds. This preference is retained albeit diminished 4-fold for the E310A mutant, but the reason for this is unclear. Here, a crystal structure of the E310A-octane complex disclosed that noncovalent interactions maintain heme deformation in the absence of the ester linkage. Consistent with the lower symmetry of the heme, resonance Raman (RR) spectroscopy revealed large enhancements of RR peaks for high-spin HC complexes of 4B1 and the E310A mutant relative to P450 3A4. Whereas these enhancements were diminished in RR spectra of a low-spin 4B1- N -hydroxy- N '-(4-butyl-2-methylphenyl)formamidine complex, a crystal structure indicated that this inhibitor does not alter heme ruffling. RR spectra of Fe 2+ -CO HC complexes revealed larger effects of HC length in E310A than in 4B1, suggesting that reduced rigidity probably underlies increased E310A-catalyzed (ω-1)-hydroxylation. Diminished effects of the HC on the position of the Fe-CO stretching mode in 4B1 suggested that the ester linkage limits substrate access to the CO. Heme ruffling probably facilitates autocatalytic ester formation by reducing inhibitory coordination of Glu-310 with the heme iron. This also positions the 5-methyl for a reaction with the proposed glutamyl radical intermediate and potentially enhances oxo-ferryl intermediate reactivity for generation of the glutamyl radical to initiate ester bond formation and ω-hydroxylation., (© 2018 Jennings et al.)

Cytochrome P450 19 (CYP19, aromatase) catalyzes the conversion of androgens to estrogens in a sequence of three reactions that each depend on NADPH and O 2 . Aromatase is a phylogenetically-ancient enzyme and its breadth of expression in other species has highlighted distinct physiological functions. In songbirds, estrogen production is required for programming the neural circuits controlling song and in the determination of sex in fish and reptiles. This work describes the expression, purification, and biophysical characterization of Aptenodytes forsteri (Emperor penguin, af) aromatase. Using human cytochrome P450 reductase as a redox partner, afCYP19 displayed similar substrate turnover and LC/MS/MS confirmed that afCYP19 catalyzes the transformations through the intermediates 19-hydroxy- and 19-oxo-androstenedione. Androstenedione and anastrozole had the highest affinity for the enzyme and were followed closely by 19-hydroxyandrostenedione and testosterone. The affinity of 19-oxo-androstenedione for afCYP19 was ten-fold lower. The time-dependent changes in the Soret bands observed in stopped-flow mixing experiments of the steroidal ligands and the inhibitor anastrozole with afCYP19 were best described by a two-step binding mechanism. In summary, these studies describe the first biophysical characterization of an avian aromatase that displays strikingly similar enzyme kinetics and ligand binding properties to the human enzyme and could serve as a convenient model system for studies of the enigmatic transformation of androgens to estrogens., (Copyright © 2018 Elsevier Inc. All rights reserved.)

The photosynthetic protein, photosystem I (PSI), has been used as a photoactive species within a host of biohybrid photoelectrochemical systems. PSI multilayer films at electrode surfaces provide greatly improved solar energy conversion relative to homologous monolayer films. While the photocatalytic effect of PSI multilayers has been theorized as an electrolyte-mediated mechanism, no comprehensive, first-principles modeling study has been presented. In this work, we develop and optimize an electrochemical reaction-diffusion model to replicate the significant electrochemical, physicochemical, and transport processes that underpin photocurrent development of a PSI multilayer film. We use this model to provide strong evidence that PSI's terminal cofactors rapidly exchange electrons with diffusible mediators and stimulate photocurrent principally due to alteration of mediator concentrations at a solution-electrode interface as governed by Butler-Volmer kinetics. Our fitted model accurately replicates photocurrent trends under a variety of conditions, including variable applied bias and PSI multilayer film thickness.

Surface-attached polydicyclopentadiene (pDCPD) films were prepared on gold and silicon substrates via surface-initiated ring-opening metathesis polymerization (SI-ROMP) of dicyclopentadiene (DCPD). The films were grown utilizing monomer in both the vapor phase and the solution phase with the former process exhibiting rapid kinetics, producing ∼400-nm-thick pDCPD films in less than 1 min of polymerization. No significant differences in thickness were observed for films grown from monomer in the vapor phase with the different isomers (exo and endo) of DCPD. Decane was used as an inert additive to control the concentration of DCPD monomer in the vapor phase enabling the preparation of pDCPD films with thickness ranging from tens of nanometers to hundreds of nanometers. The thickness of pDCPD films polymerized using monomer in the vapor phase was enhanced by the presence of a rinse solvent on the surface of the ROMP-active gold substrates. The choice of ROMP catalyst was found to be an important consideration when SI-ROMP was conducted on different substrates. Electrochemical impedance spectroscopy was used to reveal that the films provide effective barriers to the diffusion of aqueous ions in excess of 1 × 10 6 Ω·cm 2 . The mechanical properties of the surface-tethered pDCPD films were quantified with AFM PeakForce quantitative nanomechanical mapping (QNM) with a measured reduced Young's modulus (E r ) of 15 GPa. The measured E r was greater than that of a non-cross-linked surface-tethered polymer, pNB, indicating that the pDCPD films are stiffer.

Photosystem I (PSI) achieves photo-induced charge separation with outstanding internal quantum efficiency and has been used to improve the performance of various photoelectrochemical systems. Herein, we describe a fast and versatile technique to assemble composite films containing PSI and a chosen intrinsically conductive polymer (ICP). A mixture of PSI and a Friedel-Crafts catalyst (FeCl 3 ) is drop cast atop a substrate of choice. Contact with ICP monomer vapor at low temperature stimulates polymer growth throughout PSI films in minutes. We assess the effects of PSI loading on the rapid vapor-phase growth of poly(3,4-ethylenedioxythiophene) (PEDOT) within and above PSI multilayer films, and characterize the resulting film's thickness, electrochemical capacitance, and photocatalytic response. Composite films generate cathodic photocurrent when in contact with an aqueous redox electrolyte, confirming retention of the photocatalytic activity of the polymer-entrapped PSI multilayer assembly.

Recent advances in cell-based, high-throughput phenotypic screening have identified new chemical compounds that are active against eukaryotic pathogens. A challenge to their future development lies in identifying these compounds' molecular targets and binding modes. In particular, subsequent structure-based chemical optimization and target-based screening require a detailed understanding of the binding event. Here, we use directed evolution and whole-genome sequencing of a drug-sensitive S. cerevisiae strain to identify the yeast ortholog of TcCyp51, lanosterol-14-alpha-demethylase (TcCyp51), as the target of MMV001239, a benzamide compound with activity against Trypanosoma cruzi, the etiological agent of Chagas disease. We show that parasites treated with MMV0001239 phenocopy parasites treated with another TcCyp51 inhibitor, posaconazole, accumulating both lanosterol and eburicol. Direct drug-protein binding of MMV0001239 was confirmed through spectrophotometric binding assays and X-ray crystallography, revealing a binding site shared with other antitrypanosomal compounds that target Cyp51. These studies provide a new probe chemotype for TcCyp51 inhibition.

Cytochrome P450 3A4 (CYP3A4) is the dominant P450 enzyme involved in human drug metabolism, and its inhibition may result in adverse interactions or, conversely, favorably reduce the systemic elimination rates of poorly bioavailable drugs. Herein we describe a spectroscopic investigation of the interaction of CYP3A4 with N-methylritonavir, an analog of ritonavir, widely used as a pharmacoenhancer. In contrast to ritonavir, the binding affinity of N-methylritonavir for CYP3A4 is pH-dependent. At pH <7.4, the spectra are definitively type I, whereas at pH ≥7.4 the spectra have split Soret bands, including a red-shifted component characteristic of a P450-carbene complex. Variable-pH UV-visible spectroscopy binding studies with molecular fragments narrows the source of this pH dependence to its N-methylthiazolium fragment. The C2 proton of this group is acidic, and variable-pH resonance Raman spectroscopy tentatively assigns it a pKa of 7.4. Hence, this fragment of N-methylritonavir is expected to be readily deprotonated under physiologic conditions to yield a thiazol-2-ylidene, which is an N-heterocyclic carbene that has high-affinity for and is presumed to be subsequently captured by the heme iron. This mechanism is supported by time-dependent density functional theory with an active site model that accurately reproduces distinguishing features of the experimental UV-visible spectra of N-methylritonavir bound to CYP3A4. Finally, density functional theory calculations support that this novel interaction is as strong as the tightest-binding azaheterocycles found in P450 inhibitors and could offer new avenues for inhibitor development., (Copyright © 2016 by The American Society for Pharmacology and Experimental Therapeutics.)

The interface between photoactive biological materials with two distinct semiconducting electrodes is challenging both to develop and analyze. Building off of our previous work using films of photosystem I (PSI) on p-doped silicon, we have deposited a crystalline zinc oxide (ZnO) anode using confined-plume chemical deposition (CPCD). We demonstrate the ability of CPCD to deposit crystalline ZnO without damage to the PSI biomaterial. Using electrochemical techniques, we were able to probe this complex semiconductor-biological interface. Finally, as a proof of concept, a solid-state photovoltaic device consisting of p-doped silicon, PSI, ZnO, and ITO was constructed and evaluated.

We investigate near-field energy transfer between chemically synthesized quantum dots (QDs) and two-dimensional semiconductors. We fabricate devices in which electrostatically gated semiconducting monolayer molybdenum disulfide (MoS2) is placed atop a homogeneous self-assembled layer of core-shell CdSSe QDs. We demonstrate efficient nonradiative Förster resonant energy transfer (FRET) from QDs into MoS2 and prove that modest gate-induced variation in the excitonic absorption of MoS2 leads to large (∼500%) changes in the FRET rate. This in turn allows for up to ∼75% electrical modulation of QD photoluminescence intensity. The hybrid QD/MoS2 devices operate within a small voltage range, allow for continuous modification of the QD photoluminescence intensity, and can be used for selective tuning of QDs emitting in the visible-IR range.

In this work, we report for the first time the entrapment of the biomolecular supercomplex Photosystem I (PSI) within a conductive polymer network of polyaniline via electrochemical copolymerization. Composite polymer-protein films were prepared on gold electrodes through potentiostatic electropolymerization from a single aqueous solution containing both aniline and PSI. This study demonstrates the controllable integration of large membrane proteins into rapidly prepared composite films, the entrapment of such proteins was observed through photoelectrochemical analysis. PSI's unique function as a highly efficient biomolecular photodiode generated a significant enhancement in photocurrent generation for the PSI-loaded polyaniline films, compared to pristine polyaniline films, and dropcast PSI films. A comprehensive study was then performed to separately evaluate film thickness and PSI concentration in the initial polymerization solution and their effects on the net photocurrent of this novel material. The best performing composite films were prepared with 0.1 μM PSI in the polymerization solution and deposited to a film thickness of 185 nm, resulting in an average photocurrent density of 5.7 μA cm(-2) with an efficiency of 0.005%. This photocurrent output represents an enhancement greater than 2-fold over bare polyaniline films and 200-fold over a traditional PSI multilayer film of comparable thickness.

Aromatase (CYP19A1), the enzyme that converts androgens to estrogens, is of significant mechanistic and therapeutic interest. Crystal structures and computational studies of this enzyme shed light on the critical role of Asp(309) in substrate binding and catalysis. These studies predicted an elevated pK(a) for Asp(309) and proposed that protonation of this residue was required for function. In this study, UV-visible absorption, circular dichroism, resonance Raman spectroscopy, and enzyme kinetics were used to study the impact of pH on aromatase structure and androstenedione binding. Spectroscopic studies demonstrate that androstenedione binding is pH-dependent, whereas, in contrast, the D309N mutant retains its ability to bind to androstenedione across the entire pH range studied. Neither pH nor mutation perturbed the secondary structure or heme environment. The origin of the observed pH dependence was further narrowed to the protonation equilibria of Asp(309) with a parallel set of spectroscopic studies using exemestane and anastrozole. Because exemestane interacts with Asp(309) based on its co-crystal structure with the enzyme, its binding is pH-dependent. Aromatase binding to anastrozole is pH-independent, consistent with the hypothesis that this ligand exploits a distinct set of interactions in the active site. In summary, we assign the apparent pK(a) of 8.2 observed for androstenedione binding to the side chain of Asp(309). To our knowledge, this work represents the first experimental assignment of a pK(a) value to a residue in a cytochrome P450. This value is in agreement with theoretical calculations (7.7-8.1) despite the reliance of the computational methods on the conformational snapshots provided by crystal structures., (© 2015 by The American Society for Biochemistry and Molecular Biology, Inc.)

Micromolding surface-initiated polymerization enables the fabrication of polymer coatings that reproduce the microscale surface topography of superhydrophobic leaves onto solid supports. Here, the surfaces of superhydrophobic leaves from Trifolium repens and Aristolochia esperanzae are molded and reproduced as the topography of a partially fluorinated polymer coating through the surface-initiated ring-opening metathesis polymerization of 5-(perfluorooctyl)norbornene (NBF8). The polymer coatings have thicknesses exceeding 100 μm, which can be tailored by the amount of monomer added to the mold. These coatings are robustly bound to the substrate, contain compositions not found in nature, and achieve superhydrophobicity that is comparable to the actual leaf., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Over the course of a few billion years, nature has developed extraordinary nanomaterials for the efficient conversion of solar energy into chemical energy. One of these materials, photosystem I (PSI), functions as a photodiode capable of generating a charge separation with nearly perfect quantum efficiency. Because of the favorable properties and natural abundance of PSI, researchers around the world have begun to study how this protein complex can be integrated into modern solar energy conversion devices. This feature article describes some of the recent materials and methods that have led to dramatic improvements (over several orders of magnitude) in the photocurrents and photovoltages of biohybrid electrodes based on PSI, with an emphasis on the research activities in our laboratory.

Photosystem I (PSI) is a photoactive electron-transport protein found in plants that participates in the process of photosynthesis. Because of PSI's abundance in nature and its efficiency with charge transfer and separation, there is a great interest in applying the protein in photoactive electrodes. Here, we developed a completely organic, transparent, conductive electrode using reduced graphene oxide (RGO) on which a multilayer of PSI could be deposited. The resulting photoactive electrode demonstrated current densities comparable to that of a gold electrode modified with a multilayer film of PSI and significantly higher than that of a graphene electrode modified with a monolayer film of PSI. The relatively large photocurrents produced by integrating PSI with RGO and using an opaque, organic mediator can be applied to the facile production of more economic solar energy conversion devices.

The acidic residues of the "acid-alcohol pair" in CYP51 enzymes are uniformly replaced with histidine. Herein, we adopt the Mycobacterium tuberculosis (mt) enzyme as a model system to investigate these residues' roles in finely tuning the heme conformation, iron spin state, and formation and decay of the oxyferrous enzyme. Properties of the mtCYP51 and the T260A, T260V, and H259A mutants were interrogated using UV-Vis and resonance Raman spectroscopies. Evidence supports that these mutations induce comprehensive changes in the heme environment. The heme iron spin states are differentially sensitive to the binding of the substrate, dihydrolanosterol (DHL). DHL and clotrimazole perturb the local environments of the heme vinyl and propionate substituents. Molecular dynamics (MD) simulations of the DHL-enzyme complexes support that the observed perturbations are attributable to changes in the DHL binding mode. Furthermore, the rates of the oxyferrous formation were measured using stopped-flow methods. These studies demonstrate that both HT mutations and DHL modulate the rates of oxyferrous formation. Paradoxically, the binding rate to the H259A mutant-DHL complex was approximately four-fold that of mtCYP51, a phenomenon that is predicted to result from the creation of an additional diffusion channel from loss of the H259-E173 ion pair in the mutant. Oxyferrous enzyme auto-oxidation rates were relatively constant, with the exception of the T260V-DHL complex. MD simulations lead us to speculate that this behavior may be attributed to the distortion of the heme macrocycle by the substrate., (Copyright © 2014 Elsevier Inc. All rights reserved.)

This article reports the enhanced rate of the surface-initiated polymerization (SIP) of 5-(perfluoro-n-alkyl)norbornenes (NBFn) by combining two SIP techniques, namely surface-initiated atom-transfer polymerization (SI-ATRP) to grow a macroinitiator and surface-initiated ring-opening metathesis polymerization (SI-ROMP) to produce the final coating. This polymerization approach promotes the rapid growth of dense partially fluorinated coatings that are highly hydrophobic and oleophobic and yield thicknesses from 4-12 μm. Specifically, the growth rate and the limiting thickness of pNBFn with different side chain lengths (n = 4, 6, 8, and 10) at various monomer concentrations and temperatures are evaluated through two approaches: growing the polymer from an initiator-terminated monolayer (control) or from a modified poly(2-hydroxyethyl methacrylate) (PHEMA) macroinitiator. X-ray photoelectron spectroscopy (XPS) analysis shows that 38% of the hydroxyl termini in the macroinitiator react with a norbornenyl diacid chloride (NBDAC) molecule, and 7% of such anchored norbornenyl groups react with a catalyst molecule. The kinetic data have been modeled to determine the propagation velocity and the termination rate constant. The PHEMA macroinitiator provides thicker films and faster growth as compared to the monolayer, achieving a 12 μm thick coating of pNBF8 in 15 min. Increasing the monomer side chain length, n, from 4 to 10 improves the growth rate and the limiting polymer thickness. Performing the polymerization process at higher temperature increases the growth rate and the limiting thickness as evidenced by an increase in the film growth rate constant. Arrhenius plots show that the reactions involved in the macroinitiation process exhibit lower activation energies than those formed from a monolayer. Electrochemical impedance spectroscopy reveals that the films exhibit resistance against ion transport in excess of 1 × 10(10) Ω·cm(2).

We introduce the use of a hydroborated polyisoprene (PIP) macroinitiator for the rapid surface-initiated growth of superhydrophobic polymethylene (PM) films. Rinsing of a dip-coated PIP film on a methyl-terminated surface atop silicon or gold substrates results in robustly bound, isolated PIP clusters. After hydroboration of the internal olefins, these clusters result in extremely rapid growth of polymethylene coatings upon exposure to a diazomethane solution in diethyl ether at -17 °C. The resulting PM films achieve 6 μm thicknesses within 20 min of polymerization and become superhydrophobic with advancing and receding water contact angles of 166° and 156°, respectively, within 1 min. The PM films grown from these PIP clusters exhibit 3× greater propagation velocities, 30% lower termination rates, and more highly textured morphologies than PM films grown from hydroborated monolayers.

We report the fabrication of a hybrid light-harvesting electrode consisting of photosystem I (PSI) proteins extracted from spinach and adsorbed as a monolayer onto electrically contacted, large-area graphene. The transparency of graphene supports the choice of an opaque mediator at elevated concentrations. For example, we report a photocurrent of 550 nA/cm(2) from a monolayer of PSI on graphene in the presence of 20 mM methylene blue, which yields an opaque blue solution. The PSI-modified graphene electrode has a total thickness of less than 10 nm and demonstrates photoactivity that is an order of magnitude larger than that for unmodified graphene, establishing the feasibility of conjoining these nanomaterials as potential constructs in next-generation photovoltaic devices.

Tuning the Fermi energy of silicon through doping leads to alignment of silicon bands with the redox active sites of photosystem I. Integrating photosystem I films with p-doped silicon results in the highest reported photocurrent enhancement for a biohybrid electrode based on photosystem I., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Photosystem I (PSI) is a membrane protein complex that generates photoinduced electrons and transfers them across the thylakoid membrane during photosynthesis. The PSI complex, separated from spinach leaves, was spread onto the air-water interface as a monolayer and transferred onto a gold electrode surface that was precoated with a self-assembled monolayer (SAM). The electrochemical properties of the transferred PSI monolayer, including cyclic voltammetry and photoinduced chronoamperometry, were measured. The results showed that PSI retained its bioactivity after the manipulation. Its capability of converting photoenergy into electrical potential was demonstrated by its reducing an electron acceptor, dichloroindophenol (DCIP), and by oxidizing an electron donor, sodium ascorbate (ASC). We have shown that the protein has two possible orientations at the water interface. The orientation distribution was determined by comparing the controlled reductive and oxidative photocurrents generated from Langmuir-Blodgett and Langmuir-Schaefer monolayers.

Because of small surface area to volume ratios nanoscale devices can exhibit dominant surface forces that can quickly degrade unlubricated contacting surfaces. While fluorinated materials have been widely used as lubricants, because of their low critical surface tension and high thermal and mechanical stability, fluorinated monolayer coatings, which are suitable for lubricating nanoscale devices, are less effective as lubricants. Although fluorinated monolayers are more stable than their hydrocarbon counterparts against elevated temperature and humidity, they are known to exhibit higher frictional forces. To overcome this issue, here we study mixed monolayers composed of both hydrocarbon and fluorocarbon chains. Hydrocarbon-based monolayers have been widely studied and shown to improve frictional properties and device life. To investigate the frictional behavior of mixed fluorocarbon/hydrocarbon monolayers, molecular dynamics simulations of pure hydrogenated and fluorinated chains and mixed fluorinated/hydrogenated chains on silica surfaces have been performed. The adhesion and friction between the nanoconfined monolayers as a function of normal load, chain length, and chemical composition of the monolayer coating have been investigated, and mixed fluorocarbon/hydrocarbon monolayers found to outperform both pure fluorocarbon and pure hydrocarbon monolayers. Surface coverage was found to have a significant effect on the performance of all systems studied with higher surface coverage resulting in lower frictional forces. The simulations also show that when the hydrocarbon chains in the monolayer are longer than the fluorocarbon chains, a liquidlike layer is formed by the longer hydrocarbon chains that protrudes above the shorter fluorocarbon chains and aids in friction reduction. A frictional load dependence is also seen in these mixed monolayer systems because of repulsive interactions between the fluorocarbon base layer and the hydrocarbon liquidlike layer. A chain length difference of eight carbons between the base layer and the liquidlike layer was found to provide the lowest friction, while both a larger (because of increased entanglement) and a smaller (insufficient atoms between the contacting base layers to form a liquidlike layer) chain length difference increased friction.

Monolayers presenting methyl-terminated (hydrophobic) and hydroxyl-terminated (hydrophilic) surfaces on silica have been studied by molecular dynamics simulation and the effects of hydrogen bonding, chain length, and chain mixing on the frictional properties determined. The hydroxyl-terminated monolayers were found to show large adhesion zones as a result of strong interfacial interlayer hydrogen bonds; the interfacial sliding forces observed in the hydroxyl-terminated monolayers being one order of magnitude higher than the interfacial forces for the hydrophobic surfaces at the characteristic point of zero-load. Mixed hydroxyl- and methyl-terminated monolayers of equal length were found to exhibit intermediate shear stress values between those observed for pure monolayers, with the magnitude of the shear stress depending on the surface content of the hydroxyl-terminated chains. For mixed monolayers of unequal chain lengths, at high loads a maximum in the magnitude of the shear stress as a function of the length of the methyl-terminated chain was observed due to the creation of a buffer zone between the hydroxyl-terminated chains that produces strong hydrogen-bonding interactions. The effect of a constant normal load or constant separation simulation ensemble on the results has also been studied and in general found to have minimal influence on the observed behavior, although some differences are observed for the shear stress at intermediate normal loads due to the formation of stronger hydrogen bond networks at constant load compared to constant separation.

Using the abundance of available electrons generated by immobilized multilayers of the photoactive protein complex Photosystem I (PSI), we have photoreduced platinum particles that are catalytically active for the H(2)/H(+) redox couple. The resulting platinized PSI films were optimized using electrochemical measurements and then characterized using X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), and scanning electrochemical microscopy (SECM). These results demonstrate a novel method for generating immobilized platinum catalysts that are readily available on the surface of a photoactive PSI multilayer.

We report the use of atomically thin layers of graphene as a protective coating that inhibits corrosion of underlying metals. Here, we employ electrochemical methods to study the corrosion inhibition of copper and nickel by either growing graphene on these metals, or by mechanically transferring multilayer graphene onto them. Cyclic voltammetry measurements reveal that the graphene coating effectively suppresses metal oxidation and oxygen reduction. Electrochemical impedance spectroscopy measurements suggest that while graphene itself is not damaged, the metal under it is corroded at cracks in the graphene film. Finally, we use Tafel analysis to quantify the corrosion rates of samples with and without graphene coatings. These results indicate that copper films coated with graphene grown via chemical vapor deposition are corroded 7 times slower in an aerated Na(2)SO(4) solution as compared to the corrosion rate of bare copper. Tafel analysis reveals that nickel with a multilayer graphene film grown on it corrodes 20 times slower while nickel surfaces coated with four layers of mechanically transferred graphene corrode 4 times slower than bare nickel. These findings establish graphene as the thinnest known corrosion-protecting coating.

This manuscript describes the versatile fabrication and characterization of a novel composite membrane that consists of a porous alumina support, a 100 nm thick nanoporous gold coating, and a selective poly(5-(perfluorohexyl)norbornene) (pNBF6) polymer that can be grown exclusively from the nanoporous gold or throughout the membrane. Integration of the three materials is achieved by means of silane and thiol chemistry, and the use of surface-initiated ring-opening metathesis polymerization (SI-ROMP) to grow the pNBF6. The use of SI-ROMP allows tailoring of the extent of polymerization of pNBF6 throughout the structure by varying polymerization time. Scanning electron microscopy (SEM) images indicate that the thin polymer films cover the structure entirely. Cross-sectional SEM images of the membrane not only corroborate growth of the pNBF6 polymer within both the porous alumina and the nanoporous gold coating but also show the growth of a pNBF6 layer between these porous substrates that lifts the nanoporous gold coating away from the alumina. Advancing contact angle (θ(A)) measurements show that the surfaces of these composite membranes exhibit both hydrophobic (θ(A) = 121-129)° and oleophobic (θ(A) = 69-74)° behavior due to the fluorocarbon side chains of the pNBF6 polymer that dominate the surface. Results from electrochemical impedance spectroscopy (EIS) confirm that the membranes provide effective barriers to aqueous ions, as evidenced by a resistive impedance on the order of 1 × 10(7) Ω cm(2). Sulfonation of the polymer backbone substantially enhances ion transport through the composite membrane, as indicated by a 40-60 fold reduction in resistive impedance. Ion transport and selectivity of the membrane change by regulating the polymerization time. The fluorinated nature of the sulfonated polymer renders the membrane selective toward molecules with similar chemical characteristics.

We have investigated the impedance behavior of immersed superhydrophobic (SH) polymethylene surfaces by tailoring the surface tension of the contacting liquid phase to gradually transition the surface from the Cassie to the Wenzel state. Control over the surface tension is accomplished by varying the ethanol content of the aqueous phase. To establish the mechanism of the transition, we imaged the interface of the film and identified three distinct events of this process: a nucleation event at low concentrations of ethanol in which small areas beneath the liquid phase transition into the Wenzel state, a propagation event characterized by the enlargement of the Wenzel domains and the lateral displacement of air, and a final event at higher concentrations of ethanol in which the thin air layer at the interface morphs into isolated pockets of air. Using this visualization of the transition, we characterized the Cassie and the Wenzel states by measuring the impedance at a frequency of 1 kHz for an initially SH film that changes its wetting behavior upon addition of ethanol. Establishment of the Cassie and Wenzel state conditions was based on concepts of electrochemical impedance spectroscopy (EIS) and quantitatively validated using both the Helmholtz theory and the analytical description of the electrochemical system in terms of the circuit model of a metal surface covered by a polymer film. Finally, we apply this strategy to determine the possibility for SH polymethylene (PM) films to reversibly transition between the Cassie and the Wenzel states. Results show that after rinsing and drying at ambient conditions for 24 h, the film recovers the SH state, suggesting the applicability of these SH films in outdoor environments with occasional periodic submersion in water.

We demonstrate large area two-dimensional arrays of patterned nanoporous gold for use as easy-to-fabricate, cost-effective, and stable surface enhanced Raman scattering (SERS) templates. Using a simple one-step direct imprinting process, subwavelength nanoporous gold (NPG) gratings are defined by densifying appropriate regions of a NPG film. Both the densified NPG and the two-dimensional grating pattern are shown to contribute to the SERS enhancement. The resulting substrates exhibit uniform SERS enhancement factors of at least 10(7) for a monolayer of adsorbed benzenethiol molecules.

We report the frictional performance and long-term tribological stability of various alkyl silane monolayer films on silicon by using pin-on-disk tribometry at ambient conditions. We show that the durability of monolayers derived from n-alkyltrichlorosilanes on silicon increases exponentially with the chain length of the silane precursor, which we relate to the cohesive energy of these monolayers through molecular dynamics simulations. X-ray photoelectron spectroscopy (XPS) was used to show that tribological damage consisted of the loss of molecular components that could be partially replaced upon exposure to a solution containing perfluorinated silane precursors. For monolayers derived from n-octadecyltrichlorosilane, a critical load was identified to be approximately 250 mN (200 MPa), above which failure of films occurred within 100 cycles of testing. Monolayers with hydroxyl surfaces exhibited reduced stabilities due to stronger tip-surface interactions. Monolayers with the capability for cross-linking exhibited much greater stabilities than monolayers where cross-linking was limited or prevented. Collectively, these results demonstrate that the mechanical durability of monolayers when subjected to a tribological load is greatly enhanced by maximizing dispersional interactions and cross-linking and minimizing tip-surface interactions.

Photosystem I (PSI), a photoactive protein complex that participates in the light reactions of natural photosynthesis, can exhibit photocatalytic capabilities when incorporated to electrochemical systems. Here we present a simulation for the photoelectrochemical behavior of an electrode modified with a monolayer of Photosystem I complexes during photochronoamperometric experiments in which the electrode is exposed to periods of darkness and irradiation. A kinetic model is derived from conservation statements for the various oxidation states of the reaction centers of PSI complexes and electrochemical mediators within the system. The kinetic parameters that dictate the performance of the simulation are extracted from experimental data and the resulting simulation is capable of predicting the photochronoamperometric behavior of the system over a range of overpotentials. The model is used to investigate the various contributions to the photocurrent production of the system as well as the effects of the orientation of PSI complexes adsorbed to the electrode surface.

Hydrophobic coatings on carbon paper electrodes are known to provide effective water management, superior gas transfer, and improved mechanical stability of the paper in fuel cell applications. Here, we describe the surface-initiated ring-opening metathesis polymerization (ROMP) of 5-(perfluorohexyl)norbornene (NBF6) to prepare fluorocarbon-rich films on carbon paper substrates that were pre-treated with O(2) plasma. For our reaction scheme, the growth of the pNBF6 films is dependent on the concentration of hydroxyl groups on the carbon paper substrate. X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were used to determine the required time for O(2) plasma exposure to saturate the surface with hydroxyl-termini. Complete, conformal pNBF6 films were grown on carbon paper electrodes exposed to O(2) plasma for at least 45 s. These films exhibit hydrophobic and oleophobic surface properties and serve as insulative barriers to the diffusion of aqueous ions to the conductive carbon fibers., (Copyright 2010 Elsevier Inc. All rights reserved.)

Superhydrophobic polymethylene (PM) films provide remarkable protection against the transport of aqueous redox probes as a result of entrapped air at the water/polymer interface. The wetting properties and the topography for a set of superhydrophobic (SH) and nonsuperhydrophobic (NSH) PM films were established to compare their interfacial behavior using electrochemical impedance spectroscopy (EIS). EIS results show that SH PM films exhibit resistances against ion transfer that are approximately 3 orders of magnitude higher than those of NSH PM films. Rationalization of these results in the context of the Helmholtz theory reveals that the imaginary impedance or inverse capacitance of SH PM films exhibits positive deviations from that predicted by Helmholtz theory for smooth PM films. Here, we model the capacitance behavior of a SH film as a PM/air composite that acts as a circuit of capacitors. The resulting mathematical model of this analysis enables correlation of the effective dielectric properties of the film (d(effective), epsilon(effective)) to measurable properties such as thickness (d(film)) and the dielectric constant (epsilon(PM)) of the PM film. Finally, a sensitivity analysis shows that the limited contact area between the aqueous solution and PM in SH films is the primary reason for the enhancement in the barrier properties of the film.

We report a new surface-initiated polymerization strategy that yields superhydrophobic polymethylene (PM) films from initially smooth substrates of gold and silicon. The films are prepared by assembling a vinyl-terminated self-assembled monolayer, followed by exposure of the surface to a 0.1 M solution of borane, and polymerizing from the borane sites upon exposure to a solution of diazomethane at -17 degrees C. Surface-initiated polymethylenation (SIPM) presents rapid growth in relation to other surface-initiated reactions, producing PM films thicker than 500 nm after 2 min of reaction and 3 microm after 24 h of reaction. AFM and SEM images show the presence of micro- and nanoscale features that enable the entrapment of air when exposed to water. Consistent with this result, these films exhibit advancing water contact angles greater than 160 degrees, dramatically different than 103 degrees measured for smooth PM films, and hysteresis values ranging from 2 degrees to 40 degrees, depending on the substrate and polymerization time. The superhydrophobic character of the films results in the entrapment of air at the polymer/solution interface to provide remarkable resistances greater than 10(10) Omega x cm(2) against the transport of aqueous redox probes and cause the film to behave as a "perfect" capacitor.

The ability to chemically wire ionomer films to electrode surfaces can promote transport near interfaces and impact a host of energy-related applications. Here, we demonstrate proof-of-concept principles for the surface-initiated ring-opening metathesis polymerization (SI-ROMP) of norbornene (NB), 5-butylnorbornene (NBH4), and 5-perfluorobutylnorbornene (NBF4) from Pt-modified gold substrates and the subsequent sulfonation of olefins along the polymer backbones to produce ultrathin sulfonated polymer films. Prior to sulfonation, the films are hydrophobic and exhibit large barriers against ion transport, but sulfonation dramatically reduces the resistance of the films by providing pathways for proton diffusion. Sulfonated films derived from NBF4 and NBH4 yield more anodic potentials for oxygen reduction than those derived from NB or unfunctionalized electrodes. These improvements are consistent with hydrophobic structuring by the fluorocarbon or hydrocarbon side groups to minimize interfacial flooding and generate pathways for enhanced O(2) permeation near the interface. Importantly, we demonstrate that the sulfonated polymer chains remain anchored to the surface during voltammetry for oxygen reduction whereas short-chain thiolates that do not tether polymer are removed from the substrate. This approach, which we extend to unmodified gold electrodes at neutral pH, presents a method of cleaning the ionomer/electrode interface to remove molecular components that may hamper the performance of the electrode.

This Article presents a quantitative comparison of the frictional performance for monolayers derived from n-alkanethiolates on gold and n-alkyl trichlorosilanes on silicon. Monolayers were characterized by pin-on-disk tribometry, contact angle analysis, ellipsometry, and electrochemical impedance spectroscopy (EIS). Pin-on-disk microtribometry provided frictional analysis at applied normal loads from 10 to 1000 mN at a speed of 0.1 mm/s. At low loads (10 mN), methyl-terminated n-alkanethiolate self-assembled monolayers (SAMs) exhibited a 3-fold improvement in coefficient of friction over SAMs with hydroxyl- or carboxylic-acid-terminated surfaces. For monolayers prepared from both n-alkanethiols on gold and n-alkyl trichlorosilanes on silicon, a critical chain length of at least eight carbons is required for beneficial tribological performance at an applied load of 9.8 mN. Evidence for disruption of chemisorbed alkanethiolate SAMs with chain lengths n

The effect of 1-n-butyl-3-methylimidazolium nitrate ionic liquid (IL) on the shear dynamics and tribological properties of contacting ordered alkylsilane self-assembled monolayers (SAM) on SiO(2) surfaces was studied using molecular dynamics simulation. Use of the IL as a lubricant was found to reduce the friction between the contacting monolayers in the studied range of applied loads. At low applied loads, complex behavior in the dependency of the frictional force on the normal load in both lubricated and dry monolayers is observed and is shown to be due to the rearrangement of the SAM chains under shear. In contrast, this dependency was found to be linear at high normal loads. The simulations also indicate that the ordering of the SAM chains may be disrupted by penetrating lubricant molecules, suggesting that the IL could incorporate into a damaged area of the SAM coating and restore tribological properties. To our knowledge, this is the first simulation study of the effect of an IL lubricant on the frictional dynamics of SAMs.

Plants and some types of bacteria demonstrate an elegant means to capitalize on the superabundance of solar energy that reaches our planet with their energy conversion process called photosynthesis. Seeking to harness Nature's optimization of this process, we have devised a biomimetic photonic energy conversion system that makes use of the photoactive protein complex Photosystem I, immobilized on the surface of nanoporous gold leaf (NPGL) electrodes, to drive a photoinduced electric current through an electrochemical cell. The intent of this study is to further the understanding of how the useful functionality of these naturally mass-produced, biological light-harvesting complexes can be integrated with nonbiological materials. Here, we show that the protein complexes retain their photonic energy conversion functionality after attachment to the nanoporous electrode surface and, further, that the additional PSI/electrode interfacial area provided by the NPGL allows for an increase in PSI-mediated electron transfer with respect to an analogous 2D system if the pores are sufficiently enlarged by dealloying. This increase of interfacial area is pertinent for other applications involving electron transfer between phases; thus, we also report on the widely accessible and scalable method by which the NPGL electrode films used in this study are fabricated and attached to glass and Au/Si supports and demonstrate their adaptability by modification with various self-assembled monolayers. Finally, we demonstrate that the magnitude of the PSI-catalyzed photocurrents provided by the NPGL electrode films is dependent upon the intensity of the light used to irradiate the electrodes.