New techniques for the remote sensing of foliar nitrogen concentration in forest ecosystems.

During my Doctoral study I researched about the remote detection of canopy N concentration in forest stands, its potentials and problems, under many overlapping perspectives. The study consisted of three parts. In S. Rossore 2000 dataset analysis, I tested regressions between N concentration and NIR reflectances derived from different sources (field samples, airborne and satellite sensors). The analysis was further expanded using a larger dataset acquired in year 2009 as part of a new campaign funded by the ESA. In both cases, a good correlation was observed between Landsat NIR, using both TM (2009) and ETM+ (2000) imagery, and N concentration measured by a CHN elemental analyzer. Concerning airborne sensors I did not obtain the same good results, mainly because of the large FOV of the two instruments, and to the anisotropy of vegetation reflectance. We also tested the relation between ground based ASD measures and nitrogen concentration, obtaining really good results. Thus, I decided to expand my study to the regional level, focusing only on field and satellite measures. I analyzed a large dataset for the whole of Catalonia, Spain; MODIS imagery was used, in consideration of its spectral characteristics and despite its rather poor spatial resolution. Also in this case a regression between nitrogen concentration and reflectances was found, but not so good as in previous experiences. Moreover, vegetation type was found to play an important role in the observed relationship. We concluded that MODIS is not the most suitable satellite sensor in realities like Italy and Catalonia, which present a patchy and inhomogeneous vegetation cover; so it could be utilized for the parameterization of eco-physiological and biogeochemical models, but not for really local nitrogen estimate. Thus multispectral sensors similar to Landsat Thematic Mapper, with better spatial resolution, could be the most appropriate sensors to estimate N concentration.

Synthesis and aplication of linear and macrocyclic nitrogen ligand

Linear and macrocyclic nitrogen ligands have been found wide application during the years. Nitrogen has a much strong association with transition-metal ions because the electron pair is partucularly available for complexing purposes. We started our investigation with the synthesis of new chiral perazamacrocycles containing four pyrrole rings. This ligand was synthesized by the [2+2]condensation of (R,R)-diaminocyclohexane and dipirranedialdehydes and was tested, after a complexation with Cu(OAc)2, in Henry reactions. The best yields (96%) and higher ee’s (96%) were obtained when the meso-substituent on the dipyrrandialdehyde was a methyl group. The positive influence of the pyrrole-containing macrocyclic structure on the efficiency/enantioselectivity of the catalytic system was demonstrated by comparison with the Henry reactions performed using analogous ligands. Henry product was obtain in good yield but only 73% of ee, when the dialdehyde unit was replaced by a triheteroaromatic dialdehye (furan-pyrrol-furan). Another well known macrocyclic ligand is calix[4]pyrrole. We decided to investigate, in collaboration with Neier’s group, the metal-coordinating properties of calix[2]pyrrole[2]pyrrolidine compounds obtained by the reduction of calix[4]pyrrole. We focused our attention on the reduction conditions, and tested different Pd supported (charcoal, grafite) catalysts at different condition. Concerning the synthesis of linear polyamine ligands. We focused our attention to the synthesis of 2-heteroaryl- and 2,5-diheteroarylpyrrolidines. The reductive amination reaction of diarylketones and aryl-substitutedketo-aldehydes with different chiral amines was exploited to prepare a small library of diastereo-enriched substituted pyrrolidines. We have also described a new synthetic route to 1,2-disubstituted 1,2,3,4-tetrahydropyrrole[1,2-a]pyrazines, which involves the diastereoselective addition of Grignard reagents to chiral oxazolidines. The best diastereoselectivity (98:2) was dependent on the nature of both the chiral auxiliary, (S)-1-phenylglycinol, and the nature of the organometallic reagent (MeMgBr).