Immobilizing a Fluorescent Dye Offers Potential to Investigate the Glass/Resin Interface

Silane coupling agents are commonly applied to glass fibers to promote fiber/resin adhesion and enhance durability in composite parts. In this study, a coupling agent multilayer on glass was doped with trace levels of the dimethylaminonitrostilbene (DMANS) fluorophore. The fluorophore was immobilized on the glass surface by tethering the molecule to a triethoxy silane coupling agent, creating the DMANS/silane coupling agent molecule (DMSCA). DMSCA was then diluted with commonly used coupling agents and grafted to a glass microscope coverslip to create a model composite interface. A 53-nm blue shift in fluorescence from the immobilized DMSCA can be followed during cure of an epoxy resin overlayer, giving this technique potential to monitor the properties of the fiber/resin interface during composite processing. Contact angle measurements on these coupling agent layers were similar in the presence or absence of the DMSCA molecule, suggesting that trace levels of the fluorescent probe did not affect the structure of the layer. The immobilized DMSCA molecule behaved similarly to the DMANS precursor in solution. Both showed longer wavelength fluorescence in more polar environments. Copyright 2000 Academic Press.     

(Z)-3-p-tolylsulfinylacrylonitrile as a chiral dienophile: diels-alder reactions with furan and acyclic dienes

The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles.     

Measurement of neutral sugars in glycoproteins as dansyl derivatives by automated high-performance liquid chromatography

Automated high-performance liquid chromatography was used to analyse dansylhydrazine derivatives of neutral sugars in unfractionated acid hydrolysates of four well-characterized glycoproteins: fetuin, ovalbumin, alpha-1-acid glycoprotein and bovine submaxillary mucin. After a simple single-step derivatization at 65 degrees C the sugar derivatives in protein hydrolysates chromatographed as single peaks on reversed-phase C18 columns. The isocratic solvent consisted of 20% (v/v) aqueous acetonitrile containing 0.01 M formic acid, 0.04 M acetic acid and 0.001 M triethylamine. The triethylamine significantly increases the sugar peak height at 254 nm. Repeated automatic sample injection without deterioration of column performance or interference from dansyl hydrazine is not possible with published methods, but was achieved by cleaning the column between each analysis with a solvent of 20% (v/v) acetonitrile and 80% (v/v) methanol. Hydrolysis with 2 M trifluoroacetic acid is superior to 2 M hydrochloric acid for both sugar recovery and convenience but must continue for 6-8 h at 105 degrees C to ensure complete sugar release. We confirmed that mannose is present in most preparations of human high-molecular-weight salivary glycoproteins, and also examined purified bovine skin proteodermatan sulphate. p-Nitrophenylhydrazine derivatives of neutral sugars are readily produced, but do not chromatograph as successfully as the dansyl derivatives while phenylhydrazine derivatives are not easily produced at 65 degrees C. Further development of the method should be possible by producing other hydrazine derivatives of neutral sugars.