Volatile components of whole and different plant parts of bastard balm (Melittis melissophyllum L., Lamiaceae) collected in Central Italy and Slovakia

The aim of this work was to trap the volatiles released from whole frozen and dry aerial parts, and, separately, from different organs (leaves, stems, corolla and calyx) of bastard balm (Melittis melissophyllum L., Lamiaceae) populations collected in Italy and Slovakia by HS-SPME, and to identify the headspace constituents responsible for the characteristic aroma impression by GC/FID and GC/MS techniques. Among more than 100 volatile components detected, the C(8) alcohol oct-1-en-3-ol, responsible for the typical mushroom-like odor, and the phenolic coumarin, with a characteristic sweet and creamy vanilla bean odor, played a major role in the aroma of whole aerial parts and different plant organ samples. In particular, dry calyx parts could be proposed as flavoring agent in food products as mushroom aroma enhancer. Multivariate chemometric techniques, such as cluster analysis and principal component analysis, were used to characterize the sample populations according to the geographical origin and processing of plant material.     

Multiscale stochastic modelling of gene expression

Stochastic phenomena in gene regulatory networks can be modelled by the chemical master equation for gene products such as mRNA and proteins. If some of these elements are present in significantly higher amounts than the rest, or if some of the reactions between these elements are substantially faster than others, it is often possible to reduce the master equation to a simpler problem using asymptotic methods. We present examples of such a procedure and analyse the relationship between the reduced models and the original.     

Synthesis of spacer-equipped di-, tri-, and the tetrasaccharide fragments of the deacetylated O-PS1 of Citrobacter gillenii O9a,9b, and a related pentasaccharide

The title rhamnooligosaccharides [alpha-D-Rhap4NAc-(1-->3)-alpha-D-Rhap4NAc-1-O-(CH(2))(5)COOMe, alpha-D-Rhap4NAc-(1-->3)-alpha-D-Rhap4NAc-(1-->3)-alpha-D-Rhap4NAc-1-O-(CH(2))(5)COOMe, alpha-D-Rhap4NAc-(1-->2)-alpha-D-Rhap4NAc-(1-->3)-alpha-D-Rhap4NAc-(1-->3)-alpha-D-Rhap4NAc-1-O-(CH(2))(5)COOMe, and alpha-D-Rhap4NAc-(1-->3)-alpha-D-Rhap4NAc-(1-->2)-alpha-D-Rhap4NAc-(1-->3)-alpha-D-Rhap4NAc-(1-->3)-alpha-D-Rhap4NAc-1-O-(CH(2))(5)COOMe] were synthesized in a stepwise fashion from 5-methoxycarbonylpentyl 4-azido-4,6-dideoxy-2-O-benzyl-alpha-D-mannopyranoside and orthogonally protected 1-thioglycoside glycosyl donors. The amorphous, final products were fully characterized as corresponding per-O-acetyl derivatives.     

Preparation of glycoconjugates by dialkyl squarate chemistry revisited

The methyl 6-hydroxyhexanoyl glycoside of lactose was treated with each of 1,2-diaminoethane or hydrazine hydrate, and the corresponding amino amide 4 and acyl hydrazide 13, were treated with each of squaric acid dimethyl, diethyl, dibutyl, and didecyl esters. The monoesters were conjugated to bovine serum albumin (BSA) at different concentrations of hapten using 0.05 and 0.5M pH 9 borate buffer. Maximum loading was achieved faster, and the conjugation efficiency was higher, when the conjugation was conducted at higher concentrations of both hapten and buffer. Conjugations involving haptens 14-17 prepared from hydrazide 13 were generally slower and less efficient than those with compounds 5-8, which were made from amino amide 4. Maintaining pH 9 during conjugation was found to be the most important factor in ensuring that the conjugation was a fast, highly efficient, and reproducible process. When the pH of the conjugation mixture fell during the reaction, resulting in decreased reaction rate or even termination of the conjugation process, the normal course of the conjugation process could be restored by addition of buffer salts. Hydrolysis studies with monoesters formed from amino amide 4 under conjugation conditions showed that decyl ester 8 was the most stable and that the methyl compound 5 was the one most readily hydrolyzed. The stability of monoesters prepared from hydrazide 13 was similar and comparable to the decyl ester prepared from 4. No definite advantage was found for the use of any of the four dialkyl squarate reagents (methyl-, ethyl-, butyl-, and decyl-) for conversion of carbohydrate derivatives to species amenable for conjugation. Nevertheless, dimethyl squarate seemed to be the most convenient reagent because it is a crystalline, easy to handle, and commercially available material with very good reactivity.     

Why do grebes cover their nests? Laboratory and field tests of two alternative hypotheses

Egg predation is a common feature influencing the reproductive success of open nesting birds. Evolutionary pressure therefore favours building cryptic, inconspicuous nests. However, these antipredatory pressures may be in conflict with thermoregulatory constraints, which select for dry nest material maintaining optimum temperature inside a nest cup during the absence of incubating parents. Here we examined possible trade-offs between nest crypsis and thermoregulation in Little Grebes (Tachybaptus ruficollis), which lay their eggs in floating nests built from wet plant material. As this species regularly covers its eggs with nest material, we experimentally examined (1) the rates of egg predation on covered and uncovered artificial nests and (2) possible thermoregulatory costs from nest covering by comparing temperature and relative humidity changes inside the nest cup. Results revealed that covering clutches is beneficial in terms of deterring predators, because uncovered eggs were more vulnerable to predation. Moreover, covering clutches also had thermoregulatory benefits because the mean temperature and relative humidity inside nest cups covered by dry or wet materials were significantly higher for covered compared to uncovered treatments. Covering clutches in Little Grebes therefore does not pose thermoregulatory costs.     

The role of MHC class I heterodimer expression in mouse ankylosing enthesopathy

 Ankylosing enthesopathy (ANKENT) is a spontaneous mouse joint disease with strikingly similar pathology to human HLA-B27-associated enthesopathies such as ankylosing spondylitis. In C57Bl/10 mice, transgenic HLA-B^*2702 as well as H2 genes have been shown to be relative risk factors for ANKENT. To investigate the role of major histocompatibility complex (MHC) class I expression in disease pathogenesis, ANKENT occurrence was compared among β₂-microglobulin (β₂m) knockout littermates with or without transgenes for HLA-B^*2702 and human β₂m. In the knockout phenotype lacking β₂m, ANKENT occurrence is significantly reduced (P = 0.016). In the absence of β₂m, B^*2702 is not detected on the cell membrane, nor does it increase the risk for ANKENT. This means that the previous finding that HLA-B^*2702 increases susceptibility to ANKENT in C57Bl/10 mice cannot be ascribed to a transgene insertion effect. Rather, in order to increase disease susceptibility, B^*2702 must be coexpressed with mouse β₂m (mo-β₂m). In contrast, when HLA-B^*2702 is expressed with β₂m of human origin, disease susceptibility is not affected. Thus, both H2^b-derived class I heterodimers and HLA-B^*2702/mo-β₂m heterodimers contribute to ANKENT susceptibility.     

Evaluation and indirect estimation of nitrate losses from the agricultural microbasin Rybárik

The long-term trends of mean monthly nitrate concentrations in stream and drainage runoff were evaluated in the experimental microbasin Rybárik (0.119 km²) at the Institute of Hydrology, Slovak Academy of Sciences, during the period 1987–2005. The results of analyses indicate a decreasing trend of nitrate concentration after the year 1989, but with relatively high losses in some years and relatively low losses in other years. This decreasing trend is mainly caused by a decrease in the use of nitrogen fertilizers. The nitrate concentration in surface runoff strongly correlates with runoff and fertilization. Based on measured data, an empirical relation was found describing the dependence of annual nitrate transport in the stream on annual runoff depth and on the annual amount of applied nitrogen fertilizers. Presented at the International Conference on Bioclimatology and Natural Hazards, Poľana nad Detvou, Slovakia, 17–20 September 2007.     

Synthesis of methyl O-(3-deoxy-3-fluoro-β- -galactopyranosyl)-(1→6)-O-β- -galactopyranosyl-(1→6)-3-deoxy-3-fluoro -β- -galactopyranoside and related n.m.r. studies

Sequential tritylation, benzoylation, and detritylation of methyl 3-deoxy-3-fluoro-β- -galactopyranoside gave crystalline methyl 2,4-di-O-benzoyl-3-deoxy-3-fluoro-β- -galactopyranoside (9), which was used as the initial nucleophile in the synthesis of the target oligosaccharide (16). Treatment of 9 with 2,3,4-tri-O-benzoyl-6-O-bromoacetyl-α- -galactopyranosyl bromide gave the corresponding disaccharide derivative 13, having a selectively removable blocking group at O-6′. Debromoacetylation of 13 afforded the disaccharide nucleophile 14 which, when treated with 2,4,6-tri-O-benzoyl-3-deoxy-3-fluoro-α- -galactopyranosyl bromide, gave the fully protected trisaccharide 15. Debenzoylation of 15 gave the title glycoside 16. Condensation reactions were performed with silver trifluoromethane-sulfonate as a promoter in the presence of sym-collidine under base-deficient conditions, and gave excellent yields of the desired β-(trans)-products. Analyses of the ¹H- and ¹³C-n.m.r. spectra, as well as determination of the J_CF and J_HF coupling constants, were made by using various one- and two-dimensional n.m.r. techniques.