Ionic Association and Mobility IV. Ionophores in Dimethylsulfoxide at 25°C

The results of conductance measurements on pyridinium picrate, tetraphenylo-sonium picrate, potassium picrate, tetraphenylantimony picrate, tetrapropylam-monium, tetrafluoroborate, tetramethylammonium hexafluorophosphate ion association noncoulombic interaction in dimethyl sulfoxide (DMSO) at 25°C in the concentration range 1–15×10^–4 M are reported. The data were analyzed by the Justice modification of the Fuoss–Hsia equation. Except for pyridinium picrate all salts studied were found to be associated.Application of the Justice Barthel–Bjerrum model of ion association permitted calculation of the noncoulombic portion of the potential of mean force, W _±. Ionic limiting conductances were calculated for six ions using known values of previously determined transport numbers. A table of most current limiting ionic conductances for a variety of ions in DMSO at 25°C has been established.     

Discrimination of components in atherosclerotic plaques from human carotid endarterectomy specimens by magnetic resonance imaging ex vivo

Specific MRI techniques have been used to determine the dimensional and compositional properties of atherosclerotic lesions in carotid endarterectomy tissues. A quantitative comparison of areas of specific features in typical tissue segments was performed using MR images and histologic images. The mean difference for the measurements by the two methods was 4.5% for the total vessel, 5.3% for the internal carotid artery lumen, and 5.0% for the external carotid lumen. For other less abundant components, the mean difference was 14.2%. For direct characterization, individual tissue components were isolated by microdissection and their T1 and T2 relaxation times measured. Highly calcified areas typically had rather short T1 (452-837 ms) and short T2 (10.4-18.4 ms). In contrast, regions enriched in lipid had much longer T1 (1,380-1,480 ms) and longer T2 (35.3-49.0 ms). Other components such as thrombus had intermediate T1 (1,180 ms) and short T2 (15.4 ms). T2 parametric imaging was used as a complementary approach for segmentation and quantitation of tissue components. In fresh tissue, several different components exhibited different T2 ranges: calcified/solid lipid (13-18 ms). cellular/ECM (9-30 ms), fluid lipid (35-40 ms): fibrous (50-60 ms). These results demonstrate the utility of MRI for identifying and quantifying specific components of atherosclerotic plaque ex vivo, and suggest its value for these measurements in vivo as well.     

II. Ionic association and mobility in propylene carbonate

Conductance data are reported for Ph₄AsPic, Ph₄PPic, Ph₄SbPic, Hex₄NPic, Bu₄PPic, Et₄NSbCl₆ in propylene carbonate at 25°C in the concentration range 1×10^–4 to 15×10^–4 M. The data were analyzed by the Justice modification of the Fuoss-Hsia equation and all salts studied were found to be associated and to form solvent separated ion pairs. Application of the Barthel-Bjerrum model of ion association permitted calculation of the non coulombic portion of the potentials of mean force, W_±. Ionic limiting equivalent conductances of six ions were calculated using known values of R₄N⁺, and Pic^– ions. Walden products of ions in propylene carbonate were examined in the light of modern ion mobility theories, including Boyd-Zwanzig, Hubbard-Onsager, and Hubbard-Kayser models of ion solvent interactions.     

On the structure of perfect sets in various topologies associated with tree forcings

We prove that the Ellentuck, Hechler and dual Ellentuck topologies are perfect isomorphic to one another. This shows that the structure of perfect sets in all these spaces is the same. We prove this by finding homeomorphic embeddings of one space into a perfect subset of another. We prove also that the space corresponding to eventually different forcing cannot contain a perfect subset homeomorphic to any of the spaces above.     

Metastability of MCM-41 and Al-MCM-41

The apparent stability of MCM-41 and Al-MCM-41 in water was appraised in a series of solubility experiments. MCM-41 is a siliceous, mesoporous material of hexagonal symmetry and exceptionally high surface area first synthesized in 1992. The dissolution experiments were carried out at several solid/water ratios: 1/200, 1/100, and 1/75. Results indicated that MCM-41 and Al-MCM-41 are more soluble than amorphous silica at ambient temperatures. Using standard thermodynamic data, a minimum Gibbs free energy of formation of -847.9 kJ/mol for MCM-41 was calculated compared to -848.85 kJ/mol for amorphous silica and -856.3 kJ/mol for quartz. X-ray diffraction (XRD) analyses of recovered solids indicated a progressive loss of crystallinity in MCM-41 and Al-MCM-41 over the 79 day dissolution experiment. BET nitrogen surface area analyses of recovered solids revealed no appreciable change in the surface area of either material after 79 days of reaction in water. Field emission scanning electron microscope (SEM) images taken of the 79 day MCM-41 sample showed some degradation of the initial structure-fine, worm-like particles.     

Cation-Coordinating Properties of Perfluoro-15-Crown-5

The coordinative properties of perfluoro-15-crown-5 with monocations were investigated using ¹⁹F NMR spectroscopy and ion-selective electrodes with perfluoro-15-crown-5 as the matrix of their sensor membranes and the fluorophilic tetrakis[3,5-bis(perfluorohexyl)phenyl]borate as ion exchanger site. The results show that perfluoro-15-crown-5 interacts weakly but significantly with Na⁺ and K⁺. Assuming 1:1 stoichiometry, the formal complexation constants were determined to be 5.5 and 1.7 M⁻¹, respectively. This weak binding is consistent with the strong electron withdrawing nature of the many fluorine atoms in the perfluorocrown ether. While perfluorinated crown ethers have been known to form host-guest complexes with the anions O₂⁻ and F⁻ in the gas-phase, this is the first study that quantitatively confirms cation binding to a perfluorocrown ether.     

2-DE proteomic analysis of the model cyanobacterium Anabaena variabilis

Cyanobacteria are photosynthetic bacteria capable of producing hydrogen and secondary metabolites with potential pharmaceutical applications. A limited number of cyanobacterial 2-DE proteomic studies have been published, most of which are based on Synechocystis sp. PCC 6803. Here, we report the use of 2-DE, ESI-MS/MS and protein bioinformatics tools to characterize the proteome of Anabaena variabilis ATCC 29413, a heterocystous nitrogen-fixing cyanobacterium that is a model organism for the study of nitrogen fixation. Using a 2-DE workflow that included the use of a detergent-based extraction buffer and 3-10 nonlinear IPG strips resulted in the identification of 254 unique proteins, with significantly better coverage of basic and low-abundance proteins that has been reported in 2-DE analyses of Synechocystis sp. A set of protein bioinformatics tools was employed to provide estimates of protein localization, hydrophobicity, abundance and other properties. The characteristics of the A. variabilis proteins identified in this study were compared against the theoretical proteome for this organism, and more generally within the cyanobacteria, to identify opportunities for further development of 2-DE-based cyanobacterial proteomics.     

Photonic crystal nanocavities in GaAs/AlGaAs with oxidised bottom cladding

We present a solution to the difficult task of removing an oxide-based hard mask from a photonic crystal fabricated in the GaAs/AlGaAs system. We use a polymer backfill technique to seal the AlGaAs layer, thereby making it inaccessible to the wet-etch solution. This allows us to use a GaAs active layer for the photonic crystal placed on an oxidised AlGaAs layer which provides mechanical and thermal support. Using this technique, we fabricated GaAs-based photonic crystal cavities and measured respectable quality factors (Q ≈ 2200) despite the intrinsic asymmetry of the system. The technique presents a viable method for producing electrically injected photonic crystal cavities for operation on a mechanically stable and thermally conducting buffer layer.     

A swept-potential electrochemical detector for flow streams

An instrument has been designed, constructed, and evaluated for electrochemical measurements in flow streams. The instrument is basically a computer-controlled potentiostat with features which are necessary for measurements in flow streams. These features include real-time graphics display, rapid transfer of data to disk storage, automated compensation for IR drop, and automated d.c. current offset. The instrument can be programmed to operate in several modes, but the primary mode of operation is rapid-sweep square-wave voltammetry. Programs are available for post-run processing of the data and display of any desired voltammogram or current vs. time plot. Any alphanumeric or display of any desired can be copied on a dot-matrix printer. Performance evaluations in unstirred solutions indicate limits of detection of less than 1 × 10^?9 M in favorable cases.