C‐phosphorylation of 2,5‐dimethyl‐N‐arylpyrroles

C‐Phosphorylation of 2,5‐dimethylpyrroles with phosphorus (III) halides has been studied. Synthetic methods have been elaborated that provide an access to 3‐phosphorylated 2,5‐dimethylpyrroles, including pyrrole‐substituted halogeno and dihalogeno phosphines; on this basis, a variety of trivalent and pentavalent phosphorus derivatives has been obtained. Ortho‐diphosphorylated 2,5‐dimethyl‐N‐arylpyrrole derivatives have been synthesized for the first time. © 1999 John Wiley & Sons, Inc. Heteroatom Chem 10:223–230, 1999     

Induction and stabilization of liquid crystal order in H-bond complexes containing non-mesogenic species

A new approach to create mesomorphic ordered systems is discussed. It is based on the idea to use noncovalent interactions in the designing of thermotropic structures by modelling lyotropic liquid crystal (LC) when the water interlayer is changed by appropriate solid substances that are able to interact with the polar part of an amphiphilic molecule without any strong change in the intermolecular interactions between the non-polar “tails”.     

Reduction of Artifacts in Capacitive Electrocardiogram Signals of Driving Subjects

The development of smart cars with e-health services allows monitoring of the health condition of the driver. Driver comfort is preserved by the use of capacitive electrodes, but the recorded signal is characterized by large artifacts. This paper proposes a method for reducing artifacts from the ECG signal recorded by capacitive electrodes (cECG) in moving subjects. Two dominant artifact types are coarse and slow-changing artifacts. Slow-changing artifacts removal by classical filtering is not feasible as the spectral bands of artifacts and cECG overlap, mostly in the band from 0.5 to 15 Hz. We developed a method for artifact removal, based on estimating the fluctuation around linear trend, for both artifact types, including a condition for determining the presence of coarse artifacts. The method was validated on cECG recorded while driving, with the artifacts predominantly due to the movements, as well as on cECG recorded while lying, where the movements were performed according to a predefined protocol. The proposed method eliminates 96% to 100% of the coarse artifacts, while the slow-changing artifacts are completely reduced for the recorded cECG signals larger than 0.3 V. The obtained results are in accordance with the opinion of medical experts. The method is intended for reliable extraction of cardiovascular parameters to monitor driver fatigue status.     

Imaging of Spontaneous Canine Mammary Tumors Using Fluorescent Contrast Agents

We present near-infrared frequency-domain photon migration imaging for the lifetime sensitive detection and localization of exogenous fluorescent contrast agents within tissue-simulating phantoms and actual tissues. We employ intensity-modulated excitation light that is expanded and delivered to the surface of a tissue or tissue-simulating phantom. The intensity-modulated fluorescence generated from within the volume propagates to the surface and is collected using a gain-modulated image-intensified charge-coupled device camera. From the spatial values of modulation amplitude and phase of the detected fluorescent light, micromolar volumes of diethylthiatricarbocyanine iodide (tau = 1.17 ns) and indocyanine green (ICG) (tau = 0.58 ns) embedded 1.0 cm deep in a tissue phantom are localized and discriminated on the basis of their lifetime differences. To demonstrate the utility of frequency-domain fluorescent measurements for imaging disease, we image the fluorescence emitted from the surface of in vivo and ex vivo canine mammary gland tissues containing lesions with preferential uptake of ICG. Pathology confirms the ability to detect spontaneous mammary tumors and regional lymph nodes amidst normal mammary tissue and fat as deep as 1.5 cm from the tissue surface.     

Active bead-linked immunoassay on protein microarrays

Protein microarrays are becoming a powerful tool in proteome, biochemical, and clinical studies. In addition to the quality of arrayed immobilized probe molecules, sensitivity of the microarray-based assay is highly dependent on the detection technique. Here we suggest four simple techniques for rapid detection of analytes bound to protein microarrays. The techniques employ functionalized magnetic and non-magnetic beads moved to, from, or along the array surface by external forces. In contrast to other labeling techniques actively controlled physical labels: (i) make detection extremely fast to allow microarray reading in seconds; (ii) provide a low background due to active removal of weakly bound beads; and (iii) provide a highly sensitive detection, since one antigen-antibody bond is capable of holding bead immobilized on the array surface. In combination with the electrophoretically assisted active immunoassay we described recently such active reading allows to reduce total indirect immunoassay time to 7-10 min while having sensitivity in the femtomolar concentration range. High speed, sensitivity, and specificity make active bead-linked detection an ideal choice in rapid high-throughput screening and in emergency diagnostics.     

Natural convection mass transfer behavior of serially connected cylindrical electrodes

Natural convection mass transfer rates at both vertical and horizontal serially connected tubes were reported using the electrochemical technique involving the measurement of limiting currents for the deposition of copper on copper cylinders from acidified cupric sulphate solutions. Measurements were carried out with: (a) one tube active; (b) two tube surfaces active; (c) three tube surfaces active.

The electrolyte concentration and a number of serial connections of tubes were varied to provide a range of GrSc extending from 5.3×10⁸ to 9.5×10¹¹. The mass transfer rates at serially connected horizontal cylinders were in good agreement with mass transfer data in the literature. Correlation of results covered both laminar and turbulent conditions separately. The mass transfer rates at serially connected vertical cylinders were controlled by the boundary layer development at the multi-electrodes. The results for vertical electrodes, which are single, serially connected two and three electrodes, were separately correlated in the turbulent region.

The results illustrate the important effect of boundary layer development in determining current distribution in multi-electrode electrochemical cells.     

Dinitrogen activation by titanium sandwich complexes

The activation of dinitrogen by titanium sandwich complexes of the general form (eta5-C5Me4R)2Ti (R = CHMe2, CMe3, SiMe3) has been systematically investigated. Low-temperature, in situ, solution infrared spectroscopy has allowed detection of monomeric bis-dinitrogen complexes of titanium that are isostructural with more familiar dicarbonyl derivatives. One example, (eta5-C5Me4CHMe2)2Ti(N2)2, has also been characterized by X-ray diffraction and reveals weakly activated dinitrogen ligands. From the solution IR data, the relative azophilicity of the titanium sandwich complexes has been established and increases with smaller cyclopentadienyl substituents.     

Kinetics of radical polymerization, LVI. Investigation of the effect of molecular inhibitors on the radical polymerization of p-methyl-styrene. c-nitroso compounds

The inhibitive effect of p-nitroso aniline derivatives was studied for the bulk polymerization of p-methyl styrene (pMS). The compounds p-nitros-N,N-dimethyl-aniline (p-NDMA), p-nitroso-N,N-diethyl-aniline (p-NDEA) and p-nitrosodiphenyl-amine (p-NDPA) are strong inhibitors of pMS polymerizations. The inhibition period is directly proportional to the initial concentration of the inhibitor; thus, no side reaction takes place. After the inhibition period the polymerization with p-NDMA and with p-NDEA proceeds at a rate equal to that of the sample without inhibitor, while p-NDPA causes a slight secondary retardation. The value of the stoichiometric coefficient (μ) is lower than the theoretical one. This stoichiometric anomaly can be interpreted in terms of the hot radical theory.     

Evolution of the Cu/ZnO methanol synthesis catalyst during its reduction and re-oxidation

Summary Cu K EXAFS studies of the structure of Cu-Zn oxide catalyst were performed for the as prepared samples, those after its activation by hydrogen and after its subsequent re-oxidation. It was found that during the primary formation of the CuZnO solid solution, the copper ions are dissolved in the extended stacking faults of the ZnO lattice as ultra-small oxide clusters. Activation by hydrogen at 473 K leads to the reduction of most copper cations to Cu⁰with the formation of nanoparticles with the characteristic size of ca. 1.6 nm. The copper metal particles were re-oxidized to Cu²⁺at 523 K in<span lang=EN-US style='mso-ansi-language:EN-US'>ahelium flow containing 0.05 vol. % oxygen. The re-oxidized cations do not form a CuO phase. Instead, they return to the extended stacking faults of ZnO. However, this time they form stripe-like clusters of square-planar coordinated copper cations.     

Diazotrifluoropropionamido-containing prenylcysteines: syntheses and applications for studying isoprenoid-protein interactions

Photoaffinity-labeled prenylcysteines (1 and 2) incorporating a diazotrifluoropropionamide-based photophore have been prepared. Photolyses of 2 in the presence of RhoGDI, a protein that interacts with prenylated proteins, and prenylcysteine-containing competitors demonstrate the effectiveness of this photoaffinity-labeled analogue as a tool for studying isoprenoid binding sites.