The correlation between the helicity (absolute conformation) of the O-heterocyclic ring of chiral 2,3-dihydrobenzo[b]furan (1) and chromane (2) derivatives and their (1)L(b) band CD was investigated. The same helicity rule was found for both unsubstituted chromophores: P/M helicity of the heterocyclic ring leads to a negative/positive CD within the (1)L(b) band. While the substitution of the fused benzene ring by achiral substituents does not change this helicity rule for the chromane chromophore, it leads to its inversion for the 2,3-dihydrobenzo[b]furan chromophores. On the basis of these observations, the published absolute configurations of natural flavonol and pterocarpan derivatives were confirmed and the configurational assignments of several natural neolignans revised.

Comparative CD and Fourier transform ir (FTIR) spectroscopic data on N-Boc protected linear peptides with or without the (Pro-Gly) beta-turn motif (e.g., Boc-Tyr-Pro-Gly-Phe-Leu-OH and Boc-Tyr-Gly-Pro-Phe-Leu-OH) are reported herein. The CD spectra, reflecting both backbone and aromatic contributions, were not found to be characteristic of the presence of beta-turns. In the amide I region of the FTIR spectra, analyzed by self-deconvolution and curve-fitting methods, the beta-turn band showed up between 1639 and 1633 cm-1 in trifluoroethanol (TFE) but only for models containing the (Pro-Gly) core. This band was also present in the spectra in chloroform but absent in dimethylsulfoxide. These findings, in agreement with recent ir data on cyclic models and 3(10)-helical polypeptides and proteins in D2O [see S. J. Prestrelski, D. M. Byler, and M. P. Thompson (1991), International Journal of Peptide and Protein Research, Vol. 37, pp. 508-512; H. H. Mantsch, A. Perczel, M. Hollósi, and G. D. Fasman (1992), FASEB Journal, Vol. 6, p. A341; H. H. Mantsch, A. Perczel, M. Hollósi, and G. Fasman (1992), Biopolymers, Vol. 33, pp. 201-207; S. M. Miick, G. V. Martinez, W. R. Fiori, A. P. Todd, and G. L. Millhauser (1992), Nature, Vol. 359, pp. 653-655], suggest that the amide I band, with a major contribution from the acceptor C = O of the 1<--4 intramolecular H bond of beta-turns, appears near or below 1640 cm-1, rather than above 1660 cm-1.(ABSTRACT TRUNCATED AT 250 WORDS)

In Arctic and Antarctic marine regions, where the temperature declines below the colligative freezing point of physiological fluids, efficient biological antifreeze agents are crucial for the survival of polar fish. One group of such agents is classified as antifreeze glycoproteins (AFGP) that usually consist of a varying number (n = 4-55) of [AAT]( n )-repeating units. The threonine side chain of each unit is glycosidically linked to β-D: -galactosyl-(1 → 3)-α-N-acetyl-D: -galactosamine. These biopolymers can be considered as biological antifreeze foldamers. A preparative route for stepwise synthesis of AFGP allows for efficient synthesis. The diglycosylated threonine building block was introduced into the peptide using microwave-enhanced solid phase synthesis. By this versatile solid phase approach, glycosylated peptides of varying sequences and lengths could be obtained. Conformational studies of the synthetic AFGP analogs were performed by circular dichroism experiments (CD). Furthermore, the foldamers were analysed microphysically according to their inhibiting effect on ice recrystallization and influence on the crystal habit.

The capability of a Support Vector Machines QSAR model to predict the antiproliferative ability of small peptides was evaluated by screening a virtual library of enkephalin-like analogs modified by incorporation of the (R,S)-(1-adamantyl)glycine (Aaa) residue. From an initial set of 390 compounds, the peptides, Tyr-Aaa-Gly-Phe-Met (2), Tyr-Aaa-Gly-Phe-Phe (3), Phe-Aaa-Gly-Phe-Phe (4) and Phe-Aaa-Gly-Phe-Met (5) were selected, synthesized and their antitumor activity was tested and compared to that of Met-enkephalin (1). The antiproliferative activity correlated with the computational prediction and with the foldamer-forming ability of the studied peptides. The most active compounds were the hydrophobic peptides, Phe-Aaa-Gly-Phe-Phe (4) and Phe-Aaa-Gly-Phe-Met (5), having a greater propensity to adopt folded structures than the other peptides.

Abstract. Aerosol water extracts and atmospheric humiclike substances (HULIS) obtained from PM 2.5 -fraction aerosol samples collected in a rural/continental background environment and in an urban environment in spring and summer, and at a tropical site that was heavily impacted by biomass burning were studied. HULIS was obtained as the water-soluble, methanol-elutable material isolated from a solid-phase extraction procedure. The mean organic matter-to-organic carbon mass conversion factor and the standard deviation of 2.04±0.06 were derived for HULIS from biomass burning. Mean atmospheric concentrations of HULIS for the rural and urban environments and for the biomass burning during daylight periods and nights, were 1.65, 2.2, 43, and 60 µg m −3 , respectively. This and other abundances indicate that intense emission sources and/or formation mechanisms of HULIS operate in biomass burning. Mean contributions of C in HULIS (HULIS-C) to watersoluble organic carbon (WSOC) were 35, 48, 63, and 76%, respectively, for the sample set listed. HULIS-C is the major component of the WSOC in tropical biomass burning. The data also suggest that HULIS most likely do not share common origin in the three environments studied. Differentiation among the possible formation processes was attempted by investigating the optical activity of HULIS through their (electronic and vibrational) circular dichroism properties. The urban HULIS did not show optical activity, which is in line with the concept of their major airborne formation from anthropogenic aromatics. The rural HULIS revealed weak optical activity, which may be associated with one of their important formation pathways by photo-oxidation and oligomerisation, i.e., with the formation from chiral biogenic precursors with one of the enantiomers slightly enriched. The The biomass burning of HULIS exhibited a strong effect in the vibrational Correspondence to: I. Salma (salma@chem.elte.hu) circular dichroism as a clear distinction from the other two types. This was related to the contribution of the thermal degradation products of lignins and cellulose. The biomass burning of HULIS resemble Suwannee River Fulvic Acid standard more closely in some aspects than the urban and rural types of HULIS, which may be related to their common origin from plant material.