Volume 25, Issue 5

Over 100 δH values of H- (P) obtained in our laboratory, as well as values from the literature, have been tabulated and discussed. These data are useful, not only in the study of molecules containing a P-H bond but also, more generally, in the determination of the factors which influence the value of proton chemical shifts.

Es wurde die Thermochromie von Lösungen des Triphenylchlormethane in Dekalin im Temperaturbereich von 25° bis 150°C untersucht. Polarisationmessungen zeigen keine Veränderung bis 110°C. Der Thermochromie ist die Bildung des Triphenylmethyl-Radikals, das sich in Anwesenheit von Luft zersetzt, zuzuschreiben. Die Reaktionsprodukte wurden identifiziert und das Reaktions-Schema angegeben.

Green’s function and partitioning techniques have been applied to the case of nitrosyl fluoride to evaluate the molecular constants. The values of the molecular constants evaluated by this procedure are, in general, in very good agreement with those obtained by the conventional normal coordinate analysis.

Several oxoplatinates (IV) and -rhenates (VII) with isolated PtO 6 or ReO 6 octahedra respectively surrounded by lithium, sodium, magnesium, calcium, strontium and barium atoms were prepared. From infrared spectra (KBr pellet technique) force constants were calculated. The values varied. depending on an inductive field effect caused by the alcaline and alcaline earth atoms, which increased in the following order: Ba<Sr<Ca ≈ ≪ Mg. By means of bond order it can be predicted that for central atoms with d 0 or d 10 configuration and with an oxidation state lower than six only such hexaoxometallates will be formed in which the alcaline or alcaline earth atoms intensity the force constant by a strong inductive effect. PtO 6 requires an additional force which lowers the symmetry of PtO 6 and stabilizes the hexaoxoplatinates (IV).

The infrared absorption of samarium (di-isopropoxy) mono dibenzoylmethide [Sm (ΟΡ r i ) 2 DBM] and samarium tris dibenzoylmethide [Sm(DBM) 3 ] in the region 4000 - 250 cm -1 have been studied. About 25 bands in each chelate have been observed and assigned to different modes of vibrations. The number of metal-oxygen vibration modes of the chelates suggest Vh and D 3 sym. metries for Sm (OP r i ) 2 DBM and Sm (DBM) 3 respectively. The relative frequency shifts of CO and CC stretching modes indicate that the metal-oxygen bonding in Sm(DBM) 3 is relatively stronger than in Sm (OP r i ) 2 DBM.

The reactions of Uranium pentaethoxide with 1,3 dicarbonyl ligands (dibenzoyl methane, ethyl 1-methyl acetoacetate, 5,5 dimethyl 1,3 cyclohexane dione (dimedone) have been studied under anhydrous conditions and the derivatives of the type U(OEt) 5-x (lig) x (where x= 1, 2 or 3) have been isolated. These derivatives interchange their ethoxy groups with tertiary butoxy groups when treated with tertiary butanol. Determination of molecular weight of soluble derivatives suggest them to be monomeric in boiling benzene.

The hindered rotation around the C -N-axis of 2-aminomethylen-,3-indandiones 1 - 6 was investigated by NMR-spectroscopy at variable temperatures. The conformation of the compounds is discussed.

The chemoluminescence-system: DNH/NaOH aq /H 2 O 2 /hemin was investigated with the help of a “stopped-flow-technique”. By use of an optical cut-off-filter the chemoluminescence- (514 nm), and the absorptionband (325 nm) resp. could be separated which proved impossible with luminol. In this way we could follow the temporal change of chemoluminescence and of absorption of DNH: the latter dropped coutinually with progress of the reaction while the chemoluminescence-intensity passed through a maximum before it decreased according to the same rate law (pseudo first order conditions as for DNH) which governs the absorption change of DNH. The oxidation of DNH is rate-determining and of first order as to DNH, H 2 O 2 and (possibly) NaOH (k 1 = 1,5·10 -3 s -1 -1 M -2 ). The kinetic interpretation of the chemoluminescence-maxima confirmed this result. The light production occurred in a very fast secondary reaction step (k 2 ≫ k 1 ) following the oxidation of the hydrazid and with H 2 O 2 participating. Diazochinone is assumed to be a primary oxidation product.

Bei der UV-Photolyse (λ= 254 nm) von 5-Joduracil (C =5·10 -4 Mol/l) in wäßriger, sauerstoffgesättigter Lösung bildet sich als organisches Produkt nur Isodialursäure. Daneben entsteht elementares Jod. H 2 O 2 wird nicht gefunden. Bei pH =1 (H 2 SO 4 ) liegt neben dem elementaren Jod zusätzlich Jod in einer höheren Oxydationsstufe vor, das aus Jodid Jod frei macht und in dessen Gegenwart zugesetztes H 2 O 2 rasch abgebaut wird. Unter besonderen Bedingungen wird nach der Photolyse bei pH =1 sehr wenig H 2 O 2 gefunden, welches beim Stehenlassen rasch aus der Lösung verschwindet. In Anwesenheit von Jodid (C=5·10 -4 Mol/l) entsteht bei pH=3,5 (H 2 SO 4 ) nur Isodialursäure und zwei Äquivalente Jod. Jod in einer anderen Wertigkeitsstufe wird nicht gefunden.

The lowest triplet states of diphenylpolyenes and of deuterated stilbenes were observed by means of photoflash asportion spectroscopy. The diphenylpolyenes do not show phosphorescence. The triplet lifetime is strongly dependent on triplet energy. This is consistent with the known influence of Franck-Condon factors. The triplet lifetime of partially deuterated stilbenes depends on the number and the position of the deuterium atoms. The effect of olefinic monodeuteration on the non-radiative process is approximately 16 times larger than that of deuteration at an aromatic position. The observations can be explained in terms of isotope effects on vibronic spin-orbit coupling.

A zero flow method of rapidly determining reflection coefficients of giant algae cells is described. Changes of the osmotic pressure in the outside medium caused a net volume flow through the cell membranes and consequently changes of the hydrostatic pressure inside the cell. By continously measuring the hydrostatic pressure it was possible, to determine the concentration outside the cell at which no volume flow occurs. The reflection coefficients of some non-electrolyts were determined on the membrane of the mediterranean algae Valonia utricularis with an error of 3 - 4% and are discussed on the basis of the pore model. The hydrostatic pressure inside Valonia cells decreased exponentially with time, when they were put into a hypertonic aequous solution. If a linear dependence of the volume (water) flow on the hydrostatic and osmotic pressure differences is supposed, it will be possible to calculate the volume (water) flow.

Es wurde das Verhalten der Flavine gegenüber einiger Psychopharmaka untersucht. Die experimentellen Resultate lassen das Vorhandensein einer Wechselwirkung zwischen den zwei Molekülen annehmen. Die Ladungsübertragung spielt in diesem Prozeß eine wichtige Rolle. Eine Beziehung zwischen den berechneten ΔG 0 und der pharmakologischen Wirkung der Droge wurde festgestellt.

In den ersten sechs Stdn. nach dem Kontakt mit Phytohämagglutinin und Antilymphozyten-Globulin erhöhen sich im Stoffwechsel der Lymphozyten die Einbauraten von 3 H-Thymidin in die DNS, von 3 H-Uridin in die RNS, von 14 C-Leucin in das Protein ebenso wie der Glucoseverbrauch, die Atmung und die Milchsäurebildung. Die Permeabilität der Zellmembran nimmt zu.

Chlorophyllins inhibit oxidative phosphorylation in rat liver mitochondria, α-ketoglutarate oxidation is more sensitive than oxidizing succinate or β-hydroxybutyrate oxidation. When chlorophyllin is present, a sudden illumination of mitochondria incubated in the dark leads to a remarkable decrease of their O 2 -comsumption. In the absence of light the inhibition is diminished but not abolished.

The activity of thymidylate kinase is correlated with DNA-synthesis in Tetrahymena. During logarithmic growth it is twice as high as in the stationary phase; in cultures synchronized by heat treatment, the activity of the enzyme increases with the onset of DNA-synthesis. After application of 5 x 10 -6 ᴍ Methotrexate, the activity of thymidylate kinase remains unchanged. There is, however, a dramatic increase in enzyme activity when the inhibition of transmethylations is circumvened by adding thymidine and proteose-peptone.

Some biochemical effects of the repeated administration to rabbits of DDT (5 mg/kg), carbaryl (5 mg/kg), and parathion (0.5 mg/kg) were studied during 222 days. No significant changes were found in the blood or urine levels of amino acids. The tubular phosphorus reabsorption remained unaltered. The blood coagulation time was considerably shortened in the treated animals. The urinary excretion of 5-hydroxy-3-indoleacetic acid (5-HIAA) and 4-hydroxy-3-methoxymandelic acid (VMA) was higher in treated animals as compared to that of controls, indicating an increased rate of metabolism of serotonin and catecholamines, respectively. This increased metabolism is in turn believed to be a consequence of increased biosynthesis and release of biogenic amines caused by a “stress mechanism” induced by the administered pesticides. The amounts of 5-HIAA and VMA returned to normal 45 days after cessation of treatment.

H. METZNER described 2 a model for the photosynthesis of green plants consisting of a) the photolysis of AgCl sensitized by chlorophyll, reaction of Cl with H 2 O to give O 2 and Cl ⊖ , and b) regeneration of Ag ⊕ by reductive cleavage of Janus Green (1) by Ag. It is shown that under reaction conditions described the latter process is of no importance the main reaction being the well-known sequence a), and in part destruction of 1 by Cl formed in the course of a).

Particles from Anacystis nidulans were obtained which - similar to preparations from spinachwere deficient in ferredoxin or in both ferredoxin and ferredoxin-NADP-reductase. The photosynthetic NADPH 2 -formation in these particles could be restored by addition of both these factors. The ferredoxin-NADP-reductase isolated from Anacystis closely ressembled in its enzymatical behaviour that enzyme from spinach. As previously described antibodies prepared against the spinach ferredoxin-NADP-reductase always inhibited the activities of the enzyme in spinach chloroplasts, regardless of whether the enzyme is bound to particles or made soluble. Contrary to this, in Anacystis these antibodies only affected the activities of the solubilized, but not of the particle-bound enzyme. Hence the reductase must be at least as tightly bound in the photosynthetic structure of Anacystis as it is in chloroplasts. The antibodies did not affect the ferredoxin-catalysed cyclic photophosphorylation in spinach and in Anacystis; this indicates that at least in spinach the ferredoxin-NADP-reductase is not involved in cyclic photophosphorylation.

Primary cercopithecus aethiops kidney cells and continuous cell lines of monkey kidneys CV-1 and BSC-1, react differently to Actinomycin-D. The effect of Actinomycin-D was measured by the incorporation of 3 H-Uridine after cells were treated similarly with the inhibitor. Both continuous cell lines exhibited, in the same way, a stronger reaction to Actinomycin-D than did the primary cells.

3 µg AC/ml cause an inhibition of cell division of E. coli K12 strains. This concentration is not mutagenic, because the reversion frequencies of the markers thr - , his - and arg - are not changed by AC treatment. However the reversion frequencies of thr - and arg - increased 1 to 4 orders of magnitude after UV irradiation, simultaneous treatment with AC and UV decreased these enlarged reversion rates at 1 exponent. The marker his - used in this experiments is not reverted by UV. The UV-sensitivity of bacterial strains with different uvr-genes is studied. The results are discussed from the view point that the influence of AC caused an inhibition of protein synthesis, whereby phenotypic expression of UV induced DNA damage is delayed and the time for repair of DNA is enlarged.

In colonies of Bombus hypnorum reared in captivity all intermediate body sizes between worker and queen are produced, the body size being determined by the amount of food for the larvae. Queens are produced, if the larvae are fed sufficiently. In captivity queens are produced at every time of the colony development, if one worker has to feed only two larvae in the maximum. In experiments where queens founded a colony together with workers, the larvae of the first brood also developed into queens. In Bombus terrestris the castes are more differentiated. Workers have a maximal body size and there are no intermediate sizes to the queen size. Larvae are determined alternatively to be workers or queens in the first 3½ days of the development. Experiments with fences show that the queen produces a pheromon which inhibits the workers from rearing new queens. Workers are not able to pass the inhibiting factor from one to another. The inhibition by the queen terminates near the end of the colony development.