Vibrational spectroscopy and crystal structure analysis of two polymorphs of the di-amino acid peptide cyclo(L-Glu-L-Glu)

Cyclo(L-Glu-L-Glu) has been crystallised in two different polymorphic forms. Both polymorphs are monoclinic, but form 1 is in space group P21 and form 2 is in space group C2. Raman scattering and FT-IR spectroscopic studies have been conducted for the N,O-protonated and deuterated derivatives. Raman spectra of orientated single crystals, solid-state and aqueous solution samples have also been recorded. The different hydrogen-bonding patterns for the two polymorphs have the greatest effect on vibrational modes with N&bond;H and C&dbond;O stretching character. DFT (B3-LYP/cc-pVDZ) calculations of the isolated cyclo(L-Glu-L-Glu) molecule predict that the minimum energy structure, assuming C2 symmetry, has a boat conformation for the diketopiperazine ring with the two L-Glu side chains being folded above the ring. The calculated geometry is in good agreement with the X-ray crystallographic structures for both polymorphs. Normal coordinate analysis has facilitated the band assignments for the experimental vibrational spectra. Copyright © 2009 John Wiley & Sons, Ltd.

Species diversity structure analysis at two sites in the tropical rain forest of Sumatra

Data from a hilly forest study site at Batang Ule, Sumatra, are organized into 30 100-m × 10-m subplots lying perpendicular to the line of maximal topographic gradient, from the valley to the plateau/ridge. The following methodological question is addressed: what species diversity measures are best used in order to reveal the ecologically distinct regions in the site. The main tool used to answer this question is the α-diversity curve (Hα). Graphical examination of tree and species densities, and α-diversity curves identifies an anomalous species diversity behaviour of the ‘ridge above the slope’ subplots which may have implications on land-facet class definitions. Factor analysis of the α-diversity curves indicates that the diversity space is two-dimensional: i.e. two diversity measures are sufficient to characterize the site; the species density (H0), and the Berger-Parker index (H[infty infinity]). In the two-dimensional diversity-space three distinct species diversity groups are found which relate to the topographic gradient at the Batang Ule site. The results are compared with those for a flat homogeneous site at Pasirmayang, Sumatra. The implications of the results on land-classifications in species-diversity mapping and conservation strategy are discussed.

Vibrational spectroscopy and DFT calculations of the di-amino acid peptide L-aspartyl-L-glutamic acid in the zwitterionic state

Solid state IR and Raman as well as aqueous solution state Raman spectra are reported for the linear di-amino acid peptide L-aspartyl-L-glutamic acid (L-Asp-L-Glu); the solution state Raman spectrum has also been obtained for the N,O-deuterated derivative. SCF-DFT calculations at the B3-LYP/cc-pVDZ level established that the structure and vibrational spectra of L-Asp-L-Glu can be interpreted using a model of the peptide with ten hydrogen-bonded water molecules, in conjunction with the conductor-like polarizable continuum solvation method. The DFT calculations resulted in the computation of a stable zwitterionic structure, which displays trans-amide conformation. The vibrational spectra were computed at the optimised molecular geometry, enabling normal coordinate analysis, which yielded satisfactory agreement with the experimental IR and Raman data. Computed potential energy distributions of the normal modes provided detailed vibrational assignments.