Micro-structural characterization of black crust and laser cleaning of building stones by micro-Raman and SEM techniques

Research concerning the formation and removal of black crusts on various historical objects is approached from many different angles. The so-called "yellowing effect", observed after laser treatment for cleaning purposes, has also received a lot of attention. Evidence regarding this phenomenon differs considerably and the actual mechanisms are still speculated on by researchers. In an attempt to elucidate the processes involved in the yellowing effect associated with laser cleaning, a new analytical technique has been used to investigate the black crust, a region of the sample cleaned by laser irradiation at 1064 nm and another region of the same sample subjected to further laser irradiation at 355 nm, on a limestone sample from the cathedral of Seville in Spain. Micro-Raman spectrometry offers the advantage of spatial chemical characterization of the stone, based upon its molecular makeup and was performed on the bulk body of the stone. Raman and scanning electron microscopy/energy dispersive X-ray spectrometry (SEM/EDXS) results indicate that the surfaces cleaned by irradiation at 1064 nm and by double irradiation at 1064 and 355 nm differed in terms of their calcium sulphate, calcium oxalate and iron oxide content, and that this could contribute to the difference in colour observed.     

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.     

Solid-Phase Synthesis of a Monofunctional trans-a(2)Pt(II) Complex Tethered to a Single-Stranded Oligonucleotide

Cross-linking ability is possible with the oligonucleotide-tethered, monofunctional trans-Pt(II) complex shown. It was synthesized by a novel solid-phase approach comprising conjugation of immobilized tetrathymidylic acid with a trans-a(2)Pt(II) building unit, ammonolysis, and transformation of the resulting complex (R=1-N-cyclohexylmethylthyminate) into the chloro derivative (R=Cl). a=NH(2)CH(3), T=thymine.     

Nutrient cycling responses to fire frequency in the Kruger National Park (South Africa) as indicated by stable isotope analysis

Fires, which are an intrinsic feature of southern African ecosystems, produce biogenic and pyrogenic losses of nitrogen (N) from plants and soils. Because of the long history of fires in these savannas, it was hypothesized that N2 fixation by legumes balances the N losses caused by fires. In this study, the N2 fixation activity of woody legumes was estimated by analyzing foliar delta15N and proportional basal area of N2 fixing species along experimental fire gradients in the Kruger National Park (South Africa). In addition, soil carbon (C) and N pools, foliar phosphorus (P) and gross N mineralization and nitrification rates were measured, to indicate the effects of fires on nutrient stocks and the possible N cycling processes modified by fires. Although observations of increased soil C/N and mineralization rates in frequently burned plots support previous reports of N losses caused by fires, soil %N did not decrease with increasing fire frequency (except in 1 plot), suggesting that N losses are replenished in burned areas. However, relative abundance and N2 fixation of woody legumes decreased with fire frequency in two of the three fire gradients analyzed, suggesting that woody legume N2 fixation is not the mechanism that balances N losses. The relatively constant %N along fire gradients suggests that these ecosystems have other mechanisms to balance the N lost by fires, which could include inputs by atmospheric deposition and N2 fixation by forbs, grasses and soil cyanobacteria. Soil isotopic signatures have been previously used to infer patterns of fire history. However, the lack of a relationship between soil delta15N and fire frequency found in this study indicates that the effects of fires on ecosystem delta15N are unpredictable. Similar soil delta15N along fire gradients may reflect the contrasting effects of increased N gaseous emissions (which increases delta15N) and N2 fixation other than that associated with woody legumes (which lowers delta15N) on isotopic signatures.