Synthesis of mannose oligosaccharides via reversal of the α-mannosidase reaction

Summary Three naturally occurring isomers of the disaccharideO--d-mannosyl-d-mannoside were synthesized by reversing the hydrolytic activity of jack bean -mannosidase at 75°C in a very high concentration of mannose. Higher oligosaccharides were also obtained at the later stages of the reaction. The maximum total yield of disaccharides was 37% (w/w) based on the total amount of saccharides.     

Structural studies on the O-specific side-chains of the cell-wall lipopolysaccharide from Escherichia coli O 75

The structure of the O-specific side-chains of the cell-wall lipopolysaccharide of Escherichia coli O 75 has been investigated, using methylation analysis and Smith degradation as the principal methods. The O-specific side-chain was found to be composed of a tetrasaccharide repeating-unit of the following structure:

     

Effects of estradiol and estradiol sulfamate on the liver of ovariectomized or ovariectomized and hypophysectomized rats

This study was performed to evaluate and compare the effects of estradiol sulfamate (J995) and estradiol (E2) on the hepatic levels of the estrogen receptor (ER) and its mRNA, in ovariectomized (OVX) and OVX+hypophysectomized (OVXHX) female rats and to study the effects on the liver-derived serum compounds angiotensin I, triglycerides, high-density lipoprotein (HDL) and cholesterol. ER concentrations were determined using ligand-binding assay (LBA) and enzyme immuno assay (EIA), and the mRNA levels using solution hybridization.

The rats were treated orally (p.o.) or subcutaneously (s.c.) for 7 days, with treatments initiated 14 days after surgery.

No differences were found in ER mRNA levels between J995 and E2 treated rats.

The s.c. administered estrogens increased ER levels in OVX rats. Addition of GH+DEX to OVXHX rats restored the ER to levels above those seen in intact rats, whereas simultaneous oral treatment with E2 significantly decreased ER levels again. The s.c. treatment with either J995 or E2 limited the increase caused by addition of GH+DEX.

After oral treatment angiotensin I levels were increased by E2, but not by J995, while triglycerides, HDL and cholesterol levels were decreased by oral E2, J995 showing a similar pattern but was less effective.

In summary, these results on hepatic ER levels and estrogen dependent compounds produced by the liver showed that J995 has a lower impact on the normal liver functions after oral treatment than E2. Thus, J995 is a very promising substance for development of oral estrogen treatment with reduced hepatic side effects.     

Synthesis and conformation of four 16,17-diols in the 3-methoxy-13alpha-estra-1,3,5(10)-triene series

All four diasteromeric 16,17-diols in the 3-methoxy-13alpha-estra-1,3,5(10)-triene series have been synthesized. The trans-diols 1 and 2 can be obtained by hydroborating the 17-enol acetate 6 (61%, ratio 27:73, preferred alpha attack). OsO(4) dihydroxylation of the olefin 7 yielded the cis-diols 3 and 4 (ratio 13:87). The dihydroxylation proceeds with preference for beta attack caused by a C-ring twist-boat form of 7. The conformations of the diols 2 and 4, the 17-benzyl-17-hydroxy compounds 9 and 10 (obtained by Grignard reaction), and the 16alpha-bromo-17beta-hydroxy compound 8 were determined by X-ray analysis and by 1H NMR spectroscopy in solution. Some compounds, in spite of a 17beta-hydroxy group, had a conformation with a ring C chair form (4, 8, 9) caused by intermolecular interaction in the solid state. The rest of the compounds studied here (2, 10) possessed a conformation with a ring C twist-boat form, which has been also found for all 17beta-substituted compounds in solution. The preferred conformation of the D-ring with 17beta-substituents seems to be the 16beta-envelope form or near this form, but the existence of the 16alpha-envelope form (inversion of the ring D) for some compounds showed great variance in the conformation of ring D, which is substituent dependent.     

The plurennial life cycles of the European Tettigoniidae (Insecta: Orthoptera)

Summary The effect of drought on embryonic development and on hatching was studied in 13 European Tettigoniidae species. Drought can affect development in three different ways: (1) Embryonic development proceeds slower than if the eggs are in contact with water; (2) it stops (for final diapause) in an earlier embryonic stage; (3) it affects maintenance and termination of the initial embryonic diapause.In many Tettigoniidae species, the initial diapause is prolonged, and may last several years. Without draught stress, between 1 and 7 cold treatments in the laboratory, and with eggs of the Tettigonia-species between 1 and 6 winters in the field were necessary to enable all eggs to complete initial diapause. In Central European species, the number of eggs maintaining initial diapause significantly increased when the eggs had no contact with water at the time when they should recover from diapause. In contrast, termination of initial diapause in Tettigonia caudata from Greece, when the environment became favorable for growth again, was highest in that group of eggs that had lost most water in a preceding period of drought. The importance of the prolonged initial diapause for the survival of unpredictable adverse conditions is discussed.     

Studies of the distribution of the 4-O-methyl-d-glucuronic acid residues in birch xylan

The distribution of the 4-O-methyl-d-glucuronic acid residues in birch xylan has been studied. Elimination of the 4-O-methyl-d-glucuronic acid residues of methylated birch-xylan was followed by specific cleavage of the xylan backbone at the originally branched d-xylose residues, using a technique involving sequential oxidation, β-elimination, and mild hydrolysis with acid. The molecular weight distribution of the resulting methylated oligosaccharides indicates that the 4-O-methyl-d-glucuronic acid residues are irregularly distributed in birch xylan.     

Effect of photoperiod on the maternal induction of an egg diapause in the grasshopper Chorthippus bornhalmi

The effect of the photoperiod experienced maternally on the induction of an egg diapause was studied in the grashopper Chorthippus bornhalmi Harz (Acridoidea: Gomphocerinae), which lives on the southern Balkan peninsula. Photoperiods used ranged from L12:D12 to L20:D4 and were kept constant, or were increased or decreased after the imaginal ecdysis in other experiments. Under most conditions in the study, the females laid almost only diapause eggs (not less than 93%). Using constant day-lengths, only at L14:D10 the percentage of non-diapause eggs was somewhat higher (20%). An increase in day-length from moderately long (L14:D10) to long day (L16:D8) was necessary for non-diapause eggs to predominate. However, the percentage of non-diapause eggs decreased with the age of the females, except when the day-length was raised a second time. An increase from short day (L12:D12) to moderately long day (L14:D10) or from long day (L16:D8) to extremely long day (L18:D6) as well as a decrease of day-length, all resulted in the production of diapause eggs. The consequences for the life cycle are discussed.

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Zusammenfassung Der einfluß der Photoperiode auf die maternelle Induktion einer Eidiapause beim Grashüpfer Chorthippus bornhalmi wurde untersucht. Die Art lebt auf der südöstlichen Balkanhalbinsel. Die getesteten Photoperioden reichten von L12:D12 bis L20:D4. In einem Teil der Versuche wurde die Photoperiode während des gesamten Lebens der Grashüpfer konstant gehalten, in anderen nach der Imaginalhäutung erhöht oder erniedrigt. Unter den meisten Bedingungen legten die Grashüpfer-Weibchen fast ausschließlich Diapause-Eier (mehr als 93%). Bei konstanten Tageslängen stieg der Anteil der Subitaneier lediglich nach einer Eiablage bei L14:D10 auf 20%. Eine Erhöhung der Photophase von 14 auf 16 Stunden war notwendig, damit der Anteil an Subitaneier überwog. Aber auch unter diesen Bedingungen nahm ihr Anteil mit dem Alter der Weibchen ab, außer wenn die Photophase noch ein zweites Mal (auf 18 Stunden) verlängert worden war. Eine Zunahme der Tageslänge von Kurztag (L12:D12) auf mäßigen Langtag (L14:D10) oder auch von Langtag (L16:D8) auf extremen Langtag (L18:D6) sowie eine Abnahme der Tageslänge hatten zur Folge, daß die Weibchen fast ausschließlich Diapause-Eier legten. Auf grund der spezialisierten Form der Diapause-Induktion können die Grashüpfer im Freiland nur im Frühjahr Subitaneier legen.

     

Characterization of a penta-and an octasaccharide from urine of a patient with juvenile GM1-gangliosidosis.

Two structurally related oligosaccharides have been isolated from the urine of a patient with GM₁-gangliosidosis type 2. The isolation procedure included ultrafiltration, gel chromatography on Sephadex G-25, and preparative paper chromatography. From structural studies including optical rotation, sugar analysis, methylation analysis, and chromium trioxide oxidation, the following structures are deduced:

The octasaccharide has previously been reported to be present in both liver and urine of patients with GM₁-gangliosidosis type 1 and type 2. The pentasaccharide is a new compound and is an integral part of the octasaccharide. The yields of the octasaccharide and pentasaccharide were 17 and 8 mg/liter of urine, respectively. Both compounds are most probably degradation products derived from the core of glycoprotein carbohydrate chains.     

Inferring species boundaries using acoustic and morphological data in the ground cricket genus Gymnogryllus (Orthoptera: Grylloidea: Gryllinae)

An important function of song production by male crickets is to attract conspecific females. These sound signals can be used to infer species boundaries as they can provide indirect evidence for reproductive isolation. However, many studies of orthopteran diversity in South-east Asia are based mainly on morphology and only occasionally acoustics. As such, there is a lack of information on how acoustic data can be congruent with morphological data when used to delineate species. Crickets of the genus Gymnogryllus (Grylloidea, Gryllidae), are such an example. Gymnogryllus are relatively speciose, but their calling songs have not been studied. We collected specimens and calling songs of five Gymnogryllus species from South-east Asia. The acoustic parameters of the calls, along with male tegminal venation and morphology genitalia, were compared. All data types showed congruency in distinguishing G. sylvestris and G. leucostictus from each other and from the other species. Inferring species boundaries for G. angustus, G. malayanus, and G. unexpectus using acoustics and tegminal morphometry proves to be more challenging. While acoustics, tegminal morphometry, and genital morphology are likely to be useful for inferring species of Gymnogryllus from different species groups, greater coverage of taxa is needed to resolve taxonomy of closely related Gymnogryllus.