RAFT "grafting-through" approach to surface-anchored polymers: Electrodeposition of an electroactive methacrylate monomer.

The synthesis of homopolymer and diblock copolymers on surfaces was demonstrated using electrodeposition of a methacrylate-functionalized carbazole dendron and subsequent reversible addition-fragmentation chain transfer (RAFT) "grafting-through" polymerization. First, the anodically electroactive carbazole dendron with methacrylate moiety (G1CzMA) was electrodeposited over a conducting surface (i.e. gold or indium tin oxide (ITO)) using cyclic voltammetry (CV). The electrodeposition process formed a crosslinked layer of carbazole units bearing exposed methacrylate moieties. This film was then used as the surface for RAFT polymerization process of methyl methacrylate (MMA), styrene (S), and tert-butyl acrylate (TBA) in the presence of a free RAFT agent and a free radical initiator, resulting in grafted polymer chains. The molecular weights and the polydispersity indices (PDI) of the sacrificial polymers were determined by gel permeation chromatography (GPC). The stages of surface modification were investigated using X-ray photoelectron spectroscopy (XPS), ellipsometry, and atomic force microscopy (AFM) to confirm the surface composition, thickness, and film morphology, respectively. UV-Vis spectroscopy also confirmed the formation of an electro-optically active crosslinked carbazole film with a [Formula: see text] - [Formula: see text] absorption band from 450-650nm. Static water contact angle measurements confirmed the changes in surface energy of the ultrathin films with each modification step. The controlled polymer growth from the conducting polymer-modified surface suggests the viability of combining electrodeposition and grafting-through approach to form functional polymer ultrathin films.

Catalyzed Reformatsky reactions with ethyl bromofluoroacetate for the synthesis of alpha-fluoro-beta-hydroxy acids.

The presence of catalytic amounts of CeCl(3) improves yields and simplifies procedure in the Reformatsky reactions of ethyl bromofluoroacetate with aldehydes and ketones to generate diastereomeric mixtures of alpha-fluoro-beta-hydroxy esters, some of which can be separated by crystallization or column flash chromatography. Diastereomerically pure alpha-fluoro-beta-hydroxy acids are obtained by mild alkaline hydrolysis of the resolved alpha-fluoro-beta-hydroxy esters. Detailed NMR data of new alpha-fluoro-beta-hydroxy esters and alpha-fluoro-beta-hydroxy acids are also presented.

Elevated proapoptotic Bax and caspase 3 activation in the NOD.scid model of Sjögren's syndrome.

OBJECTIVE: Salivary gland epithelial cells in patients with Sjögren's syndrome (SS) and in NOD and NODscid mice express Fas and Fas ligand, and these cells die from apoptosis. To elucidate the intracellular molecular mechanisms responsible for this salivary gland epithelial cell apoptosis, expression of the Bcl-2 family of proteins (Bcl-2, Bcl-xL, Bax) and caspase (caspases 3 and 8) was studied in young (ages 8-10 weeks) and old (ages 17-28 weeks) NOD and NOD.scid mice. METHODS: Sections of frozen salivary gland tissue were obtained from NOD and NOD.scid mice and from the lip biopsy material of SS patients. Immunohistochemistry or Western blot analysis was performed to assess the apoptotic-associated proteins. RESULTS: Levels of Bax and caspase 3 were elevated in the epithelial cells of glands from old NOD mice, but not in those from young NOD mice. In contrast, epithelial cells from both young and old NOD.scid mice exhibited strong expression of Bax and caspase 3. Western blot analysis showed that the activated form of caspase 3 was increased 2-5-fold in the glands from old NOD, old NOD.scid, and young NOD.scid mice compared with those from young NOD mice. Caspase 3 was also significantly elevated (P < 0.01) in SS patients whose focus scores were grade 3 or 4. In the SS patients' biopsy tissue and in the mouse glands, cells with fragmented DNA were positive for caspase 3. CONCLUSION: These results demonstrate that salivary gland epithelial cells in NOD and NOD.scid mice overexpress the proapoptotic molecules Bax and caspase 3. Bax could be the gene responsible for initiation of caspase activation, epithelial cell destruction, and lymphocyte glandular localization in SS.

Studies on the transmission of Venezuelan equine encephalitis virus by Colombian simuliidae (Diptera).

The ability of Simulium mexicanum and Simulium metallicum to serve as biological or mechanical vectors of an enzootic and an epizootic strain of Venezuelan equine encephalitis (VEE) virus was examined. Guinea pigs were inoculated with the epizootic Cordoba strain or the enzootic RPVP407 strain of VEE virus. Wild-caught adult Simuliidae were fed on the viremic guinea pigs and the virus content of groups of flies was determined at daily intervals post-engorgement to test for viral replication. Flies were refed on suckling mice at greater than or equal to 8 days post-engorgement to test for biological transmission. Other flies were interrupted while feeding on viremic guinea pigs and refed on suckling mice to test for mechanical transmission. Neither S. mexicanum nor S. metallicum appear to be efficient vectors of either strain of VEE virus, although occasional mechanical transmission was obtained. Titers of virus in flies decreased rapidly after engorgement and from 3-12 days post-engorgement virus was detected only in 5%-25% of both species of flies. Although earlier field evidence implicated both S. mexicanum and S. metallicum as vectors of epizootic VEE, we conclude that it is highly unlikely that they play an important role as vectors of the virus in nature.

Boophilus microplus tick burdens on grazing cattle in Colombia.

This study was conducted at Carimagua Research Centre in a well-drained savanna area in the eastern plains of Colombia. The objectives were to note the effect of ecological factors on tick burdens, principally the effect of the environment given by four grasses on the seasonal variations of tick populations. Adult female tick counts were carried out on heifers grazing four pastures and tick larvae on the grass detected by cloth dragging. Tick counts were significantly higher on animals grazing Brachiaria decumbens than those grazing Andropogon gayanus, Melinis minutiflora or native pastures. Tick larvae counts on the grass showed a similar tendency. Introduced grasses and intensification of production will require greater care to control tick infestations since increases in stocking rate and ground coverage could augment tick populations.