Chemistry, Department of

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Approaching the Self-Consistency Challenge of Electrocatalysis with Theory and Computation

Peer reviewed: 
Yes, item is peer reviewed.
Date created: 
2018-04-04
Abstract: 

This opinion piece centers around challenges involved in developing first- principles electrochemical methods. In recent years, theory and computation have become quintessential tools to navigate the parameter space that controls the activity and stability of electrocatalytic materials and electrochemical devices. Viable methods process as input details on materials structure, composition and reaction conditions. Their output includes metrics for stability and activity, phase diagrams, as well as mechanistic insights on reaction mechanisms and pathways. The core challenge, connecting input to output, is a self-consistency problem that couples the electrode potential to variables for the electronic structure of the solid electrode, solvent properties and ion distributions in the electrolyte as well as specific properties of a boundary region in between. We will discuss a theoretical framework and computational approaches that strive to accomplish this feat.

Document type: 
Article

Tipping Water Balance and the Pt Loading Effect in Polymer Electrolyte Fuel Cells: A Model-based Analysis

Peer reviewed: 
Yes, item is peer reviewed.
Abstract: 

The commercial deployment of polymer electrolyte fuel cells (PEFCs) hinges on breakthroughs in design and integration of highly performing and durable catalyst layers with drastically reduced platinum loading. Experimental studies have shown an unexpected increase in voltage losses upon a drastic reduction in the Pt content. In an effort to unravel this peculiar behavior, an existing physical model of catalyst layers in PEFCs is employed to analyze a wide range of fuel cell performance data from the literature. The analysis reveals correlated trends in key fuel cell parameters. These findings can be explained in view of the tipping water balance that affects the interplay of transport and reaction in catalyst layer and gas diffusion media. This represents a compelling alternative to the widespread ionomer-film hypothesis that links observed power losses at low Pt loading to a mesoscopic oxygen transport resistance. The presented theoretical analysis warrants the definition of a correlation exponent that should find use in assessing the merit of different approaches in catalyst layer fabrication.

Document type: 
Article

Morphology of Anion-Conducting Ionenes Investigated by X-ray Scattering and Simulation

Peer reviewed: 
Yes, item is peer reviewed.
Date created: 
2018-01-24
Abstract: 

We have studied the morphology of a novel series of benzimidazole-based ionenes, methylated poly(hexamethyl-p-terphenylbenzimidazolium) (HMT-PMBI), in halide form. Materials with anion-exchange capacities ranging from 0 to 2.5 mequiv/g were studied. X-ray scattering reveals three length scales in the materials: ion–polymer spacing (4 Å), polymer–polymer interchain spacing (6 Å), and an intrachain repeat distance (20 Å). No long-range structure is apparent above the monomer length, which is rare in ion-conducting polymer membranes. In preliminary molecular dynamics simulations, water molecules were observed forming chains between ions, even at a modest level of hydration, providing an interpenetrating network where conductivity can occur.

Document type: 
Article

Selecting of a Cytochrome P450cam SeSaM Library with 3-Chloroindole and Endosulfan - Identification of Mutants that Dehalogenate 3-Chloroindole

Peer reviewed: 
Yes, item is peer reviewed.
Date created: 
2017-09
Abstract: 

Cytochrome P450cam (a camphor hydroxylase) from the soil bacterium Pseudomonas putida shows potential importance in environmental applications such as the degradation of chlorinated organic pollutants. Seven P450cam mutants generated from Sequence Saturation Mutagenesis (SeSaM) and isolated by selection on minimal media with either 3-chloroindole or the insecticide endosulfan were studied for their ability to oxidize of 3-chloroindole to isatin. The wild-type enzyme did not accept 3-chloroindole as a substrate. Mutant (E156G/V247F/V253G/F256S) had the highest maximal velocity in the conversion of 3-chloroindole to isatin, whereas mutants (T56A/N116H/D297N) and (G60S/Y75H) had highest kcat/KM values. Six of the mutants had more than one mutation, and within this set, mutation of residues 297 and 179 was observed twice. Docking simulations were performed on models of the mutant enzymes; the wild-type did not accommodate 3-chloroindole in the active site, whereas all the mutants did. We propose two potential reaction pathways for dechlorination of 3-chloroindole.

Document type: 
Article

Synthesis of Heterobenzylic Fluorides

Peer reviewed: 
Yes, item is peer reviewed.
Date created: 
2018-01-17
Abstract: 

Fluorination at heterobenzylic positions can have a significant impact on basicity, lipophilicity, and metabolism of drug leads. As a consequence, the development of new methods to access heterobenzylic fluorides has particular relevance to medicinal chemistry. This Short Review provides a survey of common methods used to synthesize heterobenzylic fluorides and includes fluoride displacement reactions of previously functionalized molecules (e.g., deoxyfluorination and halide exchange) and electrophilic fluorination of resonance stabilized heterobenzylic anions. In addition, recent advances in the direct fluorination of heterobenzylic C(sp3)-H bonds and monofluoromethylation of heterocyclic C(sp2)-H bonds are presented.

Document type: 
Article

Tuning Electronic Structure To Control Manganese Nitride Activation

Peer reviewed: 
Yes, item is peer reviewed.
Date created: 
2016-11-18
Abstract: 

Investigation of a series of oxidized nitridomanganese(V) salen complexes with different para ring substituents (R = CF3, tBu, and NMe2) demonstrates that nitride activation is dictated by remote ligand electronics. For R = CF3 and tBu, oxidation affords a Mn(VI) species and nitride activation, with dinitrogen homocoupling accelerated by the more electron-withdrawing CF3 substituent. Employing an electron-donating substituent (R = NMe2) results in a localized ligand radical species that is resistant to N coupling of the nitrides and is stable in solution at both 195 and 298 K.

Document type: 
Article
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Digitized Molecular Detection on Off-the-shelf Blu-ray Discs: Upgraded Resolution and Enhanced Sensitivity

Peer reviewed: 
Yes, item is peer reviewed.
Date created: 
2017-03-22
Abstract: 

Beyond the intrinsic capability of storing and archiving high-definition movies and games, off-the-shelf Blu-ray discs have been adopted for the preparation of molecular binding assays, which are subsequently read and quantitated with a standard computer drive in conjunction with the disc-quality check program. The performance of this digitized molecular detection system has been examined first with an artificial “ink assay” (an array of microsize ink dots) to define the quantitation capability and the lateral resolution; the conventional biotin-streptavidin binding assay was then tested with the Blu-ray detection platform, and the results compared with that obtained on a DVD. The upgraded lateral resolution (<100 μm) and enhanced assay performance (linear response up to 0.4 μg/mL and LOD estimated to be >< 0.1 μg/mL for the trial biotin-streptavidin system augments its potential to be adapted as a cost-effective and quantitative diagnostic tool for on-site analysis and point-of-care medical diagnosis at trace amounts.

Document type: 
Article
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Host-guest Interaction at Molecular Interfaces: Binding of Cucurbit[7]uril on Ferrocenyl Self-assembled Monolayers on Gold

Peer reviewed: 
Yes, item is peer reviewed.
Date created: 
2017-03-22
Abstract: 

Ferrocene (Fc) encapsulated cucurbit[7]uril (CB[7]) supramolecular host-guest complex  (Fc@CB[7]) as a synthetic recognition pair has been widely adapted for coupling biomolecules and nanomaterials due to its ultra-high binding affinity. In this paper, we have explored the binding of CB[7] on binary ferrocenylundecanethiolate/octanethiolate self-assembled monolayer on gold  (FcC11S-/C8S-Au), a model system to deepen our understanding of host-guest chemistry at molecular interfaces. It has been shown that upon incubation with CB[7] solution, the redox behavior FcC11S-/C8S-Au changes remarkably, i.e., a new pair of peaks appeared at more positive potential with narrowed widths. The ease of quantitation of surface bound-redox species (Fc+/Fc and  Fc+@CB[7]/ Fc@CB[7]) enabled us to determine the thermodynamic formation constant of  Fc@CB[7] at FcC11S-/C8S-Au (7.3±1.8 × 104 M-1). With time-dependent redox responses, we were able to, for the first time, deduce both the binding and dissociation rate constants, 2.8±0.3 × 103  M-1s-1 and 0.08±0.01 s-1, respectively. These results showed substantial differences both thermodynamically and kinetically for the formation of host-guest inclusion complex at molecular interfaces with respect to solution-diffused, homogenous environments.

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Article
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Superhydrophobic Substrates from Off-The-Shelf Laboratory Filter Paper: Simplified Preparation, Patterning, and Assay Application

Peer reviewed: 
Yes, item is peer reviewed.
Date created: 
2017-09-21
Abstract: 

Off-the-shelf laboratory filter paper of different pore-sizes and thicknesses can be modified with fluorine-free organosilanes to be superhydrophobic, patternable, and ready for quantitative assay applications. In particular, we have demonstrated that cellulose filter paper treated with a binary hexane solution of short (methyltrichlorosilane, MTS) and long (octadecyltrichlorosilane, OTS) organosilanes, exhibits remarkably high water contact angles (> 150 °) and low wetting hysteresis (~10 °). Beyond the optimized ratio between the two organosilanes, we have discovered that the thickness rather than the pore size dictates the resulting superhydrophobicity. Scanning electron microscope (SEM) images showed that silianization does not damage the cellulose microfibers; instead they are coated with uniform, particulate nanostructures, which should contribute to the observed surface properties. The modified filter paper is chemically stable and mechanically durable; it can be readily patterned with UV/ozone treatment to create hydrophilic regions to prepare chemical assays for colorimetric pH and nitrite detections.

Document type: 
Article

Revealing and Resolving the Restrained Enzymatic Cleavage of DNA Self-Assembled Monolayers on Gold: Electrochemical Quantitation and ESI-MS Confirmation

Peer reviewed: 
Yes, item is peer reviewed.
Date created: 
2017-01
Abstract: 

Herein we report a combined electrochemical and ESI-MS study of the enzymatic hydrolysis efficiency of DNA self-assembled monolayers (SAMs) on gold, platform systems for understanding nucleic acid surface chemistry and for constructing DNA-based biosensors. Our electrochemical approach is based on the comparison of the amounts of surface-tethered DNA nucleotides before and after Exonuclease I (Exo I) incubation using electrostatically bound [Ru(NH3)6]3+ as redox indicators. It is surprising to reveal that the hydrolysis efficiency of ssDNA SAMs does not depend on the packing density and base sequence, and that the cleavage ends with surface-bound shorter strands (9-13 mers). The ex-situ ESI-MS observations confirmed that the hydrolysis products for ssDNA SAMs (from 24 to 56 mers) are dominated with 10-15 mer fragments, in contrast to the complete digestion in solution. Such surface-restrained hydrolysis behavior is due to the steric hindrance of the underneath electrode to the Exo I/DNA binding, which is essential for the occurrence of Exo I-catalyzed processive cleavage. More importantly, we have shown that the hydrolysis efficiency of ssDNA SAMs can be remarkably improved by adopting long alkyl linkers (locating DNA strands further away from the substrates).

Document type: 
Article
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