Interfacial properties of precipitate-based ion-selective electrodes : Rotating disk impedance measurements of the Ag2S/Ag (aqueous) interface

Three-electrode rotating disk impedance measurements were made from 31.6 kHz to 0.0178 Hz on Ag₂S/Ag⁺ (aqueous) and Ag₂S/Ag systems. Membranes were prepared from materials precipitated in excess of silver or sulfide ions, and stoichiometric mixtures. Impedances were analyzed, as a function of rotation rate and bathing activities, to isolate bulk conductivities, internal diffusion, surface kinetic and dissolution/crystallization impedances. High-frequency bulk resistivities, R_∞, varied by four with precipitation and pressing conditions. Resistivities were the same for solution and ohmic configurations for each preparation. For ohmic contacts, R_∞ and R(DC) were identical. Solution contact cells in 10^-1 M and 10^-2 M bathing silver ion solution gave identical frequency-dependent impedances which were independent of rotation rate. Thus, solution diffusional impedances and solution dependent surface kinetics were eliminated, and a finite Warburg, interior-Ag⁺-defect, diffusion impedance was indicated. Summation of bulk membrane and contact resistances, and this Warburg impedance served as a 'background' correction in analyzing dilute bathing solution interfacial impedances for surface effects. Corrected impedances in 10^-3 –10^-5 M AgNO₃ showed solution diffusional behaviour combined with surface kinetic and dissolution impedances. An iterative linear least-squares method resolved these quantities. The surface resistance suggests a potential-dependent rate constant; dissolution time constants were solution-independent and smaller than those for solution diffusion. Thus, dissolution can be a rate-limiting step in establishment of steady-state potentials.     

Pt-catalyzed cyclization/migration of propargylic alcohols for the synthesis of 3(2H)-furanones, pyrrolones, indolizines, and indolizinones

Several heterocycles such as furanones, pyrrolones, and indolizines, which are of pharmacological importance, are easily accessed via the Pt(II)-catalyzed heterocyclization/1,2-migration of propargylic ketols or hydroxy imine derivatives. This method sidesteps the challenges of traditional heteroaromatic oxygenation strategies such as regioselectivity and functional group tolerance in the syntheses of these heterocycles.     

p<Emphasis Type="Italic">K</Emphasis><Subscript>a</Subscript> measurements for the SAMPL6 prediction challenge for a set of kinase inhibitor-like fragments

Determining the net charge and protonation states populated by a small molecule in an environment of interest or the cost of altering those protonation states upon transfer to another environment is a prerequisite for predicting its physicochemical and pharmaceutical properties. The environment of interest can be aqueous, an organic solvent, a protein binding site, or a lipid bilayer. Predicting the protonation state of a small molecule is essential to predicting its interactions with biological macromolecules using computational models. Incorrectly modeling the dominant protonation state, shifts in dominant protonation state, or the population of significant mixtures of protonation states can lead to large modeling errors that degrade the accuracy of physical modeling. Low accuracy hinders the use of physical modeling approaches for molecular design. For small molecules, the acid dissociation constant (pK_a) is the primary quantity needed to determine the ionic states populated by a molecule in an aqueous solution at a given pH. As a part of SAMPL6 community challenge, we organized a blind pK_a prediction component to assess the accuracy with which contemporary pK_a prediction methods can predict this quantity, with the ultimate aim of assessing the expected impact on modeling errors this would induce. While a multitude of approaches for predicting pK_a values currently exist, predicting the pK_as of drug-like molecules can be difficult due to challenging properties such as multiple titratable sites, heterocycles, and tautomerization. For this challenge, we focused on set of 24 small molecules selected to resemble selective kinase inhibitors—an important class of therapeutics replete with titratable moieties. Using a Sirius T3 instrument that performs automated acid–base titrations, we used UV absorbance-based pK_a measurements to construct a high-quality experimental reference dataset of macroscopic pK_as for the evaluation of computational pK_a prediction methodologies that was utilized in the SAMPL6 pK_a challenge. For several compounds in which the microscopic protonation states associated with macroscopic pK_as were ambiguous, we performed follow-up NMR experiments to disambiguate the microstates involved in the transition. This dataset provides a useful standard benchmark dataset for the evaluation of pK_a prediction methodologies on kinase inhibitor-like compounds.     

Development of an Electrochemical Technique for the Removal of Ultratrace Levels of Heavy Metals from Water Using Accelerated Electrodeposition

A readily available source of ultrapure water is a basic requirement in most analytical work. The earliest requirement for ultrapure water was in electrochemical research^1. In recent years, nuclear reactors, semiconductor and electronic industries require very pure water^2,3. Ultrapure water is needed to prepare standards whenever the determination of ultratrace (ppb) concentrations of metals is required.     

Selectivity for the methoxycarbonylation of ethylene versus CO---ethylene copolymerization with catalysts based on C4-bridged bidentate phosphines and phospholes

The C₄-bridged phospholes 11,12-bis(2,3,4,5-tetramethylphospholylmethyl)-9,10-dihydro-9,10-ethano-anthracene (cis, 4a; trans, 4b) and diphosphines 11,12-bis(diphenylphosphinomethyl)-9,10-dihydro-9,10-ethano-anthracene (cis, 5a; trans, 5b) and their corresponding palladium complexes [(P---P)PdCl₂] (6a–d) have been prepared and characterized. Single-crystal X-ray analyses of 6a–d have been undertaken and they reveal that 4a and b and 5a and b coordinate in a bidentate manner forming seven-membered chelate rings with natural bite angles between 98.62 and 100.30°. The palladium-catalyzed carbonylation of ethylene has been studied using 4a and b and 5a and b. Catalyst mixtures generated from 4a and b, palladium acetate and methanesulfonic acid are selective for the copolymerization of ethylene with carbon monoxide, generating low molecular weight polymers. Surprisingly, the activity of catalyst systems based on cis-(4a) is markedly higher than that based on its trans-isomer, 4b. The marked influence of the nature of the four-carbon tether is highlighted by comparative catalyst testing with [{1,4-bis(2,3,4,5-tetramethylphospholyl)butane}Pd(OAc)₂], which rapidly decomposes under the conditions used for copolymerization. In contrast, under identical conditions catalyst mixtures formed from 5a and b show a marked dependence of the selectivity on the stereochemistry of the ethano-anthracene tether, the former generating a low molecular weight copolymer while the latter generate mainly methyl propanoate. Interestingly, polyketone generated from catalysts based on bisphosphole 4a has a markedly higher average molecular weight than that formed using its diphenylphosphino counterpart, 5a.     

Development of a biofuel cell using glucose-oxidase- and bilirubin-oxidase-based electrodes

Biofuel cells have a tremendous opportunity to provide much higher energy densities and smaller footprints than batteries for powering implantable medical devices, leading to less intrusive implantable devices with longer lifetimes. This paper introduces biofuel cell anode and cathode designs based on mediated glucose oxidation by glucose oxidase and oxygen reduction by bilirubin oxidase, respectively. We report here the progress toward the development of components for biofuel cells working in physiological conditions. We have investigated enzymatic electrode formulations that have the potential to achieve higher current densities and longer stability of the electrodes: (a) high surface area by the use of multiscale carbon materials, (b) immobilization of redox mediator on the electrode surface, and (c) use of a protective biocompatible polymer coating. Part of this work was presented at the 213th Electrochemical Society Meeting as a poster     

Microfabricated planar glass gas chromatography with photoionization detection

We report the development of a microfabricated gas chromatography system suitable for the separation of volatile organic compounds (VOCs) and compatible with use as a portable measurement device. Hydrofluoric acid etching of 95 × 95 mm Schott B270 wafers has been used to give symmetrical hemi-spherical channels within a glass substrate. Two matching glass plates were subsequently cold bonded with the channels aligned; the flatness of the glass surfaces resulted in strong bonding through van der Waals forces. The device comprised gas fluidic interconnections, injection zone and 7.5 and 1.4 m long, 320 μm internal diameter capillaries. Optical microscopy confirmed the capillaries to have fully circular channel profiles. Direct column heating and cooling could be achieved using a combination of resistive heaters and Peltier devices. The low thermal conductivity of glass allowed for multiple uniform temperature zones to be achieved within a single glass chip. Temperature control over the range 10–200 °C was achieved with peak power demand of approximately 25 W. The 7.5 m capillary column was static coated with a 2 μm film of non-polar dimethylpolysiloxane stationary phase. A standard FID and a modified lightweight 100 mW photoionization detector (PID) were coupled to the column and performance tested with gas mixtures of monoaromatic and monoterpene species at the parts per million concentration level. The low power GC-PID device showed good performance for a small set of VOCs and sub ng detection sensitivity to monoaromatics.     

OSL and IRSL characteristics of quartz and feldspar from southern California,USA

Southern California comprises of a wide range of diverse landscapes and environments, from high mountains with glacial and periglacial sediments to deserts with large sand dunes, extensive alluvial fans and ephemeral playas. Highly active tectonic processes has exposed ancient (c. 2 Ga) plutonic and metamorphic basement from deep within the crust, while similar Palaeozoic, Mesozoic and Cenozoic rocks are also common. A rich array of volcanic lithologies extending into the late Quaternary complement many thick sedimentary sequences that formed in equally diverse ancient environments typical of an accreting active continental margin. In some locations, notably in the Coachella Valley close to Palm Springs and the Salton Sea, low OSL sensitivity and poor characteristics restrict the application of the quartz SAR protocol to date late Pleistocene and Holocene fluvial sediments. In other locations such as the Malibu coastline, high sensitivity of the quartz OSL signal is observed, despite local source rocks being dominated by volcanic lithologies. Problems of poor quartz characteristics, along with uncertainty in predicting quartz OSL behavior for future dating campaigns poses a significant problem for projects, in particular for neotectonic contexts. While K-feldspar has been used extensively to date eolian and fluvial sediments in southern California, little information regarding signal stability is available. We explore the characteristics of both quartz and feldspar sub-samples from eolian, fluvial, lacustrine environments, in order to help develop mineral selection criteria for optical dating applications and clarify these issues. The importance of radiation quenching in quartz grains recently eroded from bedrock and the role of fires in enhancing OSL sensitivity are considered. The relative bleachability of quartz and feldspar fractions, along with thermal stability considerations is discussed. A simple test for quartz OSL signal contamination based on thermal quenching and assistance, and the susceptibility of the OSL signal to IR bleaching is introduced.