Identifizierung von sechs Komponenten des Spurpheromons der Ameisenart Lasius fuliginosus. Vorläufige Mitteilung

Hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, and dodecanoic acid are components of the trail pheromone of the ant species Lasius fuliginosus. The acids were extracted from the contents of the rectal ampullae and identified by the mass spectra and gas chromatographic retention times of the corresponding methyl esters.     

Trimethylsilylcyanid als Umpolungsreagens,VI. Anionische 1,4- O→C-Silylgruppen-Umlagerung

Trimethylsilyl Cyanide — A Reagent for Umpolung, VI. Anionic 1,4-O→C-Silyl Group Rearrangement The adducts 6 from substituted acroleins 5a – f and trimethylsilyl cyanide form the anions 6 _A on deprotonation at −78°C, which are silylated by trimethylsilyl chloride to 7 or (and) 8 in positions 3 or (and) 1. On warming up to room temperature, 6a _A and 6b _A undergo smoothly 1,4-O→C-silyl group rearrangements to form 13a _A and 13b _A which can be trapped by silylation. 6c – d _A decompose on warming up. Triethylsilyl instead of trimethylsilyl groups decelerate the rearrangement appreciably. Structure and configuration of the different products are determined.     

Thermoanalytical investigations on the decomposition of double salts

The melting and decomposition behaviour of carnallite was investigated in the closed system under dynamic heating conditions and in the open system under dynamic and quasi-isothermal and quasi-isobaric conditions in the temperature range between 20 and 300°. DTA heating and cooling cycles in the closed system illustrate the incongruent melting of carnallite and the occurrence of different magnesium chloride hydrate phases. The thermal decomposition under quasi-isothermal and quasi-isobaric conditions begins at a pressure of at least 100 kPa from the melt and under reduced pressure from the solid. In any case KCl · MgCl₂ · 2 H₂O is formed which is decomposed to a basic product KMgCl_2.84–2.90(OH_0.10–0.16.

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Zusammenfassung Die Schmelz- und Zersetzungseigenschaften des Carnallits wurden im geschlossenen System unter dynamischen Heizbedingungen und im offenen System under dynamischen und quasi-isothermen und quasi-isobaren Bedingungen im Temperaturbereich von 20 bis 300°C untersucht. DTA Heiz- und Kühlzyklen im geschlossenen System verdeutlichen das inkongruente Schmelzen des Carnallits und das Auftreten verschiedener Magnesiumchlorid-Hydratphasen. Die thermische Zersetzung beginnt unter quasi-isothermen und quasi-isobaren Bedingungen bei einem Druck von mindestens 100 kPa aus der Schmelze und unter verminderten Druck aus der festen Phase. Die Zersetung verläuft stets über KCl · MgCl₂ · 2 H₂O zu einem basischen Produkt KMgCl_2.84–2.90(OH)_0.10–0.16.

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— -, - V 20–300°. . - - 100 , — . KCl · l₂ · 2 ₂, Kgl_2.84–2.90()_0.10–0.16.

     

Development of a bionematicide with Paecilomyces lilacinus to control Meloidogyne incognita

Root-knot disease caused by Meloidogyne incognita is a matter of grave concern because it affects several economically important crop plants. The use of solid-state fermentation (SSF) may help to elaborate efficient formulations with fungi to be employed in the biologic control of nematodes. Attempts were made to select low-cost substrates for spore production of a strain of Paecilomyces lilacinus with known nematicide capacity. Coffee husks, cassava bagasse, and defatted soybean cake were utilized as substrates, and sugarcane bagasse was used as support. Fermentations were carried out in flasks covered with filter paper at 28°C for 10 d. The products obtained by SSF were evaluated for their nematicide activity in pot experiments containing one seedling of the plant Coleus inoculated with the nematode M. incognita. The plants were evaluated 2 mo after inoculation. Fermented products showed a reduction in the number of nematodes. The best results were obtained with defatted soybean cake, which showed almost 100% reduction in the number of nematodes; the reduction with coffee husk was 80% and with cassava bagasse was about 60%.     

Zur Kenntnis der Halogensauerstoffverbindungm

Zusammenfassung Es wurde die Kinetik der Bromatbildungsreaktion nach 3 Br₃+6 OH=8 Br+BrO₃+3 H₂O, beziehungsweise 3 Br₂+6 OH=5 Br+BrO₃+3 H₂O untersucht und gefunden, daß die Geschwindigkeit der Bromatbildung mit den Konzentrationen von Brom und Hydroxylion steigt und mit zunehmender Bromionkonzentration abnimmt. Die Werte der Potenzexponenten der Konzentrationen variieren mit der Geschwindigkeit. Neutralsalze verzögern.Es wurde ferner für die rasche Reaktion das Zeitgesetz –d[Br₃]/d=k ₁[OH]/[Br]³[Br₃]², beziehungsweise –d[Br₂]/d=k₁[OH]/[Br][Br₂]² und für die langsame Reaktion das Zeitgesetz –d[Br₃]/d=k ₂[OH]⁴/[Br]⁷[Br₃]³, beziehungsweise –d[Br₂]/d=k₂[OH]⁴/[Br]⁴[Br₂]³ wahrscheinlich gemacht. Der Temperaturkoeffizient der in einer Monophosphat-Biphosphatlösung gemessenen langsamen Reaktion ist von der Größenordnung 17.Aus den Geschwindigkeitskoeffizienten der raschen Reaktion und dem der Reaktion HBrO+OH BrO₃ läßt sich das Brom-Hypobromitgleichgewicht und aus den Koeffizienten der langsamen Reaktion und dem der Reaktion BrO₃+Br+H^. Br₂ das Brom-Bromatgleichgewicht berechnen.Vgl. die vorhergehende Arbeit.     

Quo Vadis total reflection X-ray fluorescence?

The multielement trace analytical method ‘total reflection X-ray fluorescence’ (TXRF) has become a successfully established method in the semiconductor industry, particularly, in the ultra trace element analysis of silicon wafer surfaces. TXRF applications can fulfill general industrial requirements on daily routine of monitoring wafer cleanliness up to 300 mm diameter under cleanroom conditions. Nowadays, TXRF and hyphenated TXRF methods such as ‘vapor phase decomposition (VPD)-TXRF’, i.e. TXRF with a preceding surface and acid digestion and preconcentration procedure, are automated routine techniques (‘wafer surface preparation system’, WSPS). A linear range from 10⁸ to 10¹⁴ [atoms/cm²] for some elements is regularly controlled. Instrument uptime is higher than 90%. The method is not tedious and can automatically be operated for 24 h/7 days. Elements such as S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Br, Sn, Sb, Ba and Pb are included in the software for standard peak search. The detection limits of recovered elements are between 1×10¹¹ and 1×10⁷ [atoms/cm²] depending upon X-ray excitation energy and the element of interest. For the determination of low Z elements, i.e. Na, Al and Mg, TXRF has also been extended but its implementation for routine analysis needs further research. At present, VPD-TXRF determination of light elements is viable in a range of 10⁹ [atoms/cm²]. Novel detectors such as silicon drift detectors (SDD) with an active area of 5 mm², 10 mm² or 20 mm², respectively, and multi-array detectors forming up to 70 mm² are commercially available. The first SDD with 100 mm² (!) area and integrated backside FET is working under laboratory conditions. Applications of and comparison with ICP-MS, HR-ICP-MS and SR-TXRF, an extension of TXRF capabilities with an extremely powerful energy source, are also reported.     

Facile and efficient synthesis of 6-(hydroxymethyl)purines

[reaction: see text] A facile and efficient methodology of the synthesis of 6-(hydroxymethyl)purine derivatives (bases and nucleosides) was developed based on Pd-catalyzed cross-coupling reactions of 6-halopurines with acyloxymethylzinc iodides followed by deprotection. Several title compounds are inhibitors of adenosine deaminase and exert cytostatic activity.     

Biologically active metabolites from fungi, 19: new isocoumarins and highly substituted benzoic acids from the endophytic fungus, Scytalidium sp

Six known metabolites, two new isocoumarins 4 and 8, and one new highly substituted benzoic acid derivative 9 were isolated from the ethyl acetate culture extract of a fungal endophyte, Scytalidium sp. In addition, another new benzoic acid 10 with an unusual 1,2-dicarbonyl side chain was indirectly identified from its methylated derivatives 10a-10d.     

Stabilities and Redox Properties of Cu(I) and Cu(II) Complexes with Macrocyclic Ligands Containing the N2S2 donor Set

The complexation of Cu(I) and Cu(II) by a series of 12-, 14- and 16-membered macrocyclic ligands 1–6 containing the N₂S₂ donor set has been studied potentiometrically, spectrophotometrically and voltammetrically. In the case of Cu(II), mononuclear complexes CuL²⁺ with stability constants of 10¹⁰–10¹⁵ are formed. In addition, partially hydrolyzed species Cu(L)OH⁺ are observed at pH > 10 for the 12-membered ligands. For Cu(I), beside the specis CuL⁺ with stabilities of 10¹²–10¹⁴, the unexpected formation of protonated species CuLH²⁺ was detected. In contrast to the well-known general trends in coordination chemistry, the stability of these protonated species increases relative to that of the complexes with the neutral ligand when the ring size and concomitantly the distance between neighbouring donor atoms is decreased. From the stability constants of the Cu(I)- and Cu(II)-complexes the redox potentials have been calculated and are compared to the values of E^1/2 obtained by cyclic voltammetry. Despite the identical donor set the Cu(II)/Cu(I) redox potentials of the complexes are spanning a range of 340 mV or six orders of magnitude in relative stability, reflecting the importance of subtle differences in steric requirements.