Plasma fluorination of polyolefins

ESCA and contact angle measurements were used to characterize the surfaces of Polyethylene and polypropylene films exposed to SF₆, CF₄, and C₂F₆ plasmas. None of these gases polymerized in the plasma. However, all plasma treatments grafted fluorinated functionalities directly to the polymer surfaces. SF₆ plasmas graft fluorine atoms to a polyolefin surface. CF₄ plasmas also react by a mechanism dominated by fluorine atoms, but with some contribution from CF_x-radical reactions. Although C₂F₆ does not polymerize, the mechanism of grafting is still dominated by the reactions of CF_x radicals. For all gases studied, the lack of polymerization is attributed to competitive ablation and polymerization reactions occurring under conditions of ion bombardment.     

Convolution voltammetry of metal complexes

The application of convolution potential voltammetry to questions of metal complexation is described. Theoretical relations are derived to show that the stability constants may be directly related to the shift in the peak potential of the semiderivative wave, provided the complexes are labile. Equations are also given for inert and quasilabile complexes. Stability constants for the PbCl_x and CdCl_x systems are reported, illustrating the use of convolution techniques with linear scan voltammetry and with linear scan anodic stripping voltammetry. Advantages of convolution techniques are discussed.     

The venom gland of queens of Apis mellifera (Hymenoptera, Apidae): morphology and secretory cycle

The venom gland of queens of Apis mellifera was examined through light and transmission electron microscopy and subjected to electrophoretic analyses. Virgin queens exhibited prismatic secretory cells containing large amounts of rough endoplasmic reticulum with dilated cisternae, open secretory spaces, numerous vacuoles and granules scattered in the cytoplasm, and spherical nuclei with numerous nucleoli. The secretion produced was non-refringent under polarized light and the electrophoretic analysis of glandular extracts revealed five main protein bands. In mated queens, the venom gland exhibited a high degree of degeneration. Its secretion was refringent under polarized light and one of the main bands was absent in the electrophoretic pattern obtained. The morphological aspects observed are in agreement with the function of this gland in queens, given that virgin queens use venom in battles for the dominance of the colony, a situation that occurs as soon as they emerge, while fertilized queens rarely use venom.     

The ‘preference factor’ and isotope effect in the loss of hydrogen or deuterium from labeled toluenes

Metastable ion decompositions involving the loss of hydrogen and deuterium from partially deuterated toluene ions were studied using a double focusing mass spectrometer. The electric sector voltage was adjusted so that the only ions transmitted were those which lost a particular fraction of their kinetic energy in decompositions taking place in front of the electric sector. Transitions involving loss of mass 1 or mass 2 from the molecular ions of toluene-α-d₃ and toluene-2,3,4,5,6-d₅ were studied. The results showed that in these slow reactions, the ‘preference factor’ defined as the ratio of the probability of loss of a hydrogen atom from a side-chain position to loss of a hydrogen atom from a ring position was 1.00. The ‘isotope factor,’ defined as the ratio of the probability of loss of a hydrogen atom from any position to that for the loss of a deuterium atom from the same position was found to be 3·50.     

Characterization and Application of Surface Plasmon-Enhanced Optical Diffraction from Electrodeposited Gold Nanowire Arrays

Arrays of gold nanowires formed by the process of lithographically patterned nanowire electrodeposition (LPNE) were characterized by a combination of SEM, polarized UV-visible absorption spectroscopy and optical diffraction measurements. A transverse localized surface plasmon resonance (LSPR) was observed for gold nanowire arrays with an absorption maximum (λ(max)) that varied with nanowire width. Transmission optical diffraction measurements were measured with the even and odd diffraction orders creating an alternating, out of phase sinusoidal intensity pattern characteristic of the LPNE nanowire arrays. The intensities of the even diffraction order maxima were the strongest for nanowires with a width of 115 ± 10 nm; nanowires of this width exhibit a λ(max) of 635 ± 10 nm, verifying that the transverse LSPR has enhanced the optical diffraction signal. Real time total internal reflection diffraction intensity measurements were used to monitor in situ the electrodeposition of silver monolayers onto the gold nanowire arrays.     

Attomole microarray detection of microRNAs by nanoparticle-amplified SPR imaging measurements of surface polyadenylation reactions

Multiple microRNAs (miRNAs) are detected in a microarray format using a novel approach that combines a surface enzyme reaction with nanoparticle-amplified SPR imaging (SPRI). The surface reaction of poly(A) polymerase creates poly(A) tails on miRNAs hybridized onto locked nucleic acid (LNA) microarrays. DNA-modified nanoparticles are then adsorbed onto the poly(A) tails and detected with SPRI. This ultrasensitive nanoparticle-amplified SPRI methodology can be used for miRNA profiling at attomole levels.     

Clay-supported reagents; III the intermediacy of nitrous esters in the oxidation of alcohols by clay-supported ferric nitrate.

Stereospecific intermediate nitrite formation occurs in the title reaction.     

Carbon-on-metal films for surface plasmon resonance detection of DNA arrays

Surface plasmon resonance (SPR) imaging affords label-free monitoring of biomolecule interactions in an array format. A surface plasmon conducting metal thin film is required for SPR measurements. Gold thin films are traditionally used in SPR experiments as they are readily functionalized with thiol-containing molecules through formation of a gold-sulfur bond. The lability of this gold-thiol linkage upon exposure to oxidizing conditions and ultraviolet light renders these surfaces incompatible with light-directed synthetic methods for fabricating DNA arrays. It is shown here that applying a thin carbon overlayer to the gold surface yields a chemically robust substrate that permits light-directed synthesis and also supports surface plasmons. DNA arrays fabricated on these carbon-metal substrates are used to analyze two classes of biomolecular interactions: DNA-DNA and DNA-protein. This new strategy allows the combinatorial study of binding interactions directly from native, unmodified biomolecules of interest and offers the possibility of discovering new ligands in complex mixtures such as cell lysates.