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Platinum electrodes have been electrochemically roughened (roughness factors up to 430) and evaluated for use as neural stimulation electrodes. The roughened electrodes show superior interfacial properties with increasing surface roughness. The roughened electrode (fR = 250) has a charge injection limit of 1.0 mC cm(-2) (400 μs pulse width), which is superior to that of titanium nitride (0.87 mC cm(-2)) but comparable to that of carbon nanotubes (1.0-1.6 mC cm(-2)). The surface roughness can also be optimized for different neural stimulation applications based on the available charge density at a particular pulse width of stimulation. The roughened platinum electrodes demonstrated good mechanical stability under harsh ultrasonication and electrochemical stability under continuous biphasic stimulation, indicating the potential of this biological interface to be safe and stable.

We report a systematic study of the effects of types and positions of amino acid residues of tripeptides on the formation constants logβ, acid dissociation constants pKa, and the copper coordination modes of the copper(II) complexes with 27 tripeptides formed from the amino acids glutamic acid, glycine, and histidine. logβ values were calculated from pH titrations with l mmol L(-1):1 mmol L(-1) solutions of the metal and ligand and previously reported ligand pKa values. Generalized multiplicative analysis of variance (GEMANOVA) was used to model the logβ values of the saturated, most protonated, monoprotonated, logβ(CuL) - logβ(HL), and pKa of the amide group. The resulting model of the saturated copper species has a two-term model describing an interaction between the central and the C-terminal residues plus a smaller, main effect of the N-terminal residue. The model supports the conclusion that two copper coordination modes exist depending on the absence or presence of His at the central position, giving species in which copper is coordinated via two or three fused chelate rings, respectively. The GEMANOVA model for pKamide, which is the same as that for the saturated complex, showed that Gly-Gly-His has the lowest pKamide values among the 27 tripeptides. Visible spectroscopy indicated the formation of metal-ligand dimers for tripeptides His-His-Gly and His-His-Glu, but not for His-His-His, and the formation of multiple ligand bis compexes CuL2 and Cu(HL)2 for tripeptides (Glu/Gly)-His-(Glu/Gly) and His-(Glu/Gly)-(Glu/Gly), respectively.

The influence of surface polarity and, hence, the electrical double layer on long-range electron transfer was investigated using 35 different electrode constructs. These constructs were prepared using five different lengths of ferrocene-modified alkanethiols (of general formula HS(CH2)nCONHCH2Fc where n was 7, 10, 11, 14, and 17 and Fc refers to ferrocene) mixed with an appropriate ratio of hydroxyl-terminated to methyl-terminated alkanethiols as diluents. The mixtures of diluents in different ratios served not only to separate and dilute the redox-active species but also to control the surface polarity of the self-assembled monolayer (SAM). The ratios of the three components in each SAM were 1:20:0, 1:16.6:3.4, 1:13.4:6.6, 1:10:10, 1:6.6:13.4, 1:16.6:3.4, and 1:0:20 of the ferrocene-, hydroxyl-, and methyl-terminated species, respectively. The formal redox potential and electron transfer rate constant were measured for each construct. It was found, first, that formal potentials changed according to the t...

The problem of assigning a probability of matching a number of spectra is addressed. The context is in environmental spills when an EPA needs to show that the material from a polluting spill (e.g., oil) is likely to have originated at a particular site (factory, refinery) or from a vehicle (road tanker or ship). Samples are taken from the spill, and candidate sources and are analyzed by spectroscopy (IR, fluorescence) or chromatography (GC or GC/MS). A matching algorithm is applied to pairs of spectra giving a single statistic (R). This can be a point-to-point match giving a correlation coefficient or a Euclidean distance or a derivative of these parameters. The distributions of R for same and different samples are established from existing data. For matching statistics with values in the range {0,1} corresponding to no match (0) to a perfect match (1) a beta distribution can be fitted to most data. The values of R from the match of the spectrum of a spilled oil and of each of a number of suspects are calculated and Bayes' theorem is applied to give a probability of matches between spill sample and each candidate and the probability of no match at all. The method is most effective when simple inspection of the matching parameters does not lead to an obvious conclusion; i.e., there is overlap of the distributions giving rise to dubiety of an assignment. The probability of finding a matching statistic if there were a match to the probability of finding it if there were no match, expressed as a ratio (called the likelihood ratio), is a sensitive and useful parameter to guide the analyst. It is proposed that this approach may be acceptable to a court of law and avoid challenges of apparently subjective opinion of an analyst. Examples of matching the fluorescence and infrared spectra of diesel oils are given.

Peptide-modified electrode surfaces have been shown to have excellent recognition properties for metal ions. An efficient method of screening a potential peptide for its selectivity for a given metal would involve the synthesis of the peptide directly on the electrode surface. This paper outlines a procedure in which the tripeptide Gly-Gly-His was synthesized one amino acid at a time on a gold surface modified with a self-assembled monolayer of the mixed alkanethiolates 3-mercaptopropionic acid (MPA) and 3-mercaptopropane (MP). Electrochemistry and high-resolution mass spectrometry were used to elucidate the structure of the adsorbed species and follow the synthesis. The amino acids can be attached only to MPA, but the presence of a diluting unreactive molecule of MP reduces steric crowding about the reaction center. The maximum coverage of synthesized tripeptide occurs at a ratio of MPA/MP of 1:1.

A generic fill-and-flow channel biosensor with upstream electrodes to determine the extent of interferences in the sample is described. A pair of upstream electrodes poised at a suitable potential allows both the calculation of the extent of removal of interfering agents and the effect of interfering agents at the detector electrode. A model was developed and tested that predicts the concentrations of all species throughout the channel and, hence, the current at each electrode due to each species. This enables correction of the detector electrode current and a more accurate determination of the analyte concentration. The concept was applied to a biosensor for the determination of glucose in the presence of ascorbic acid, acetamidophenol, and uric acid, as well as glucose in wine samples containing polyphenolic interfering agents.

The kinetics of irreversible adsorption has been modeled numerically for cases for which the rate-limiting process is adsorption through to those for which diffusion to the surface is rate limiting. Comparison with limiting analytical models shows that even for a system under diffusion control the Ilkovic diffusion model with rate proportional to the surface coverage does not describe the kinetics adequately. The best approximate analytical models are a simple first-order model for rate-limiting adsorption and the Ilkovic model for diffusion control. The models were compared to experimental quartz crystal microbalance data for the attachment of glucose oxidase to a self-assembled monolayer. Although none of the limiting analytical models could adequately describe the adsorption behavior of this system, excellent fits to the experimental data were obtained with the numerical model for rate-limiting adsorption with heat of adsorption proportional to coverage (Frumkin adsorption kinetics). Good agreement bet...

Students in chemistry lectures were encouraged to use Twitter.com to ask and answer questions during and after lectures. Across 12 lectures, 49 students from a total enrollment of 485 generated 112 messages, of which 68% were germane to the course. Among users and nonusers alike, 77% reported Twitter made it easier to ask questions, but 66% also reported the messages intruded on lectures.

The remarkable electrocatalytic properties and small size of carbon nanotubes make them ideal for achieving direct electron transfer to proteins, important in understanding their redox properties and in the development of biosensors. Here, we report shortened SWNTs can be aligned normal to an electrode by self-assembly and act as molecular wires to allow electrical communication between the underlying electrode and redox proteins covalently attached to the ends of the SWNTs, in this case, microperoxidase MP-11. The efficiency of the electron transfer through the SWNTs is demonstrated by electrodes modified with tubes cut to different lengths having the same electron-transfer rate constant.