bluuebunny/crossref_metadata_2025 huggingface dataset:
Kinetics of the Oxidation of Aliphatic Aldehydes by Chromic Acid
Authors: Goswami C. , Banerji K. K.
Published: February 2015

The kinetics of chromic acid oxidation of propanaldehyde, butyraldehyde and isobutyraldehyde in aq. acetic acid have been studied. The product of the oxidation is the corresponding carboxylic acid. The reaction is of first order with respect to each the acid chromate ion, HCrO4
⊖, and the aldehyde but of second order to hydrogen ion. The rate increases with proportion of acetic acid in the solution. The activation parameters for the oxidation and enolisation reactions have been evaluated. The rate of enolisation under similar condition is less than that of oxidation. A mechanism in which the first step is the rapid reversible formation of a chromate ester followed by a hydrideion transfer in the rate determining step has been suggested.
Novel Approach to the Synthesis of S-Alkyl Phosphorothioates
Authors: Zwierzak A. , Gramze R.
Published: February 2015

A simple procedure for the preparation of S-alkyl phosphorothioic acids (1) involving triethylammonium di-t-butyl phosphorothioate (2) as a thiophosphorylating agent for organic halides has been devised.
Cellular Components Specifically Labeled during Sorbose Stimulation of Sugar Transport in Neurospora
Authors: Klingmüller Walter
Published: February 2015

A number of independent systems for sugar transport in Neurospora have been postulated. An approach to identification of specific components of the sorbose transport system in ungerminated conidia pretreated with sorbose is described here. The fact that sorbose stimulates sorbose-uptake without causing germination was exploited in differential labeling experiments. Sorbose treated and untreated conidia were incubated with (3H) -leucine and (14C) -leucine respectively, and then mixed extracts fractionated on CM-cellulose at pH 4.75. Changes in the 3H/14C-ratio indicated sorbose-induced or -repressed substances. In selecting labeling conditions, care was taken to avoid errors that might arise from any differences in the internal amino acid pool size.

The investigation revealed a buffer-soluble component repressed by sorbose and a Triton-soluble component induced by sorbose. The buffer-soluble, sorbose repressible protein is discussed in connection with the phenomenon of sorbose toxicity in Neurospora. The Triton-soluble, sorbose stimulated component, probably of carotenoid nature, is considered as a possible constituent of the sorbose transport system investigated here.
Metall-Bor-Verbindungen, XII / Metal Boron Compounds, XII
Authors: Nöth Heinrich , Schäfer Helwig , Schmid Günter
Published: February 2015

Diphenylboryl stannanes [ (C6H5) 2B]4 - nSn(CH3) n (n = 0, 1, 2, 3) are produced from methyl chloro stannanes and (diphos)2Co[B(C6H5) 2] 2. However, no dibromoboryl stannanes (Br2B)4 - nSn(CH3)n could be isolated in a similar reaction using (diphos) 2Co(BBr2) 2 but they are stabilized by addition of diphos yielding the complexes (Br2B)4 - nSn(CH3)n · m diphos which contain B — P bonds.
Proton Dispersion Forces and Continuous Energy Level Distribution of Protons in the Hydrogen Bonds of Semiprotonated Poly-ʟ-histidine and with Model Substances
Authors: Zundel G. , Muehlinghaus J.
Published: February 2015

IR spectroscopic investigations were conducted with poly-L-histidine (PLH) films, hydrous imidazole and pyrazole solutions and anhydrous N-methylimidazole with respect to protonation. Continuous absorption arises with increasing protonation and is maximally intensive with PLH, imidazole and N-methylimidazole when 50% protonated. The absorption indicates the formation of ΝΗ⊕･·･·･·Ν bonds. The protons in these bonds are found in continuous energy level distribution. This continuity is due to the extremely large polarizability of symmetrical hydrogen bonds with double minimum potential well in which the proton tunnels. Thus on the one hand proton dispersion forces can arise, and on the other hand the anion fields can exert considerable influence. Both cause an energy level shift. The influence of these tunneling protons on the NH groups in PLH, imidazole and pyrazole is under discussion. The Cl⊖ ions are added to these NH groups via NH · · · Cl⊖ bonds. The CH groups in the N-methylimidazole are so acidic that CH · · · Cl⊖ bonds are formed. In the case of PLH, imidazole and N-methylimidazole, the loss of the continuous absorption at more than 50% protonation is explained by the fact that each imidazole ring then possesses a Cl⊖ ion and thus the NH⊕· · · N bonds are ruptured. With pyrazole, the continuous absorption continues to increase at 50% protonation. This is due to the fact that its pKa value is considerably less than that of the other substances. Hence H5O2
⊕ groupings are already formed preferentially before the NH⊕· · · Cl⊖ groups. The rise of the continuous absorption in the case of the imidazole solution at a 100% or higher degree of protonation can be explained likewise. The corresponding rise with N-methylimidazole is accounted for by the formation of Cl⊖H⊕· · ·Cl⊖ bonds.
Desoxyribonucleasen in Mäusenieren unter dem Einfluß von Folsäure / On the Action of Folic Acid on Deoxyribonucleases of Mouse Kidney
Authors: Tempel K.
Published: February 2015

The behaviour of the in vitro-activities of an alkaline and an acid deoxyribonuclease (DNase I and II, resp.), and of an inhibitor of DNase I of the kidney of mice, as well as of the DNA- and protein-content of kidneys and thymus, was studied in about 500 mice 4 hours to 21 days after exposure to folic acid in doses of 60 — 180 mg/kg body-weight.

The most important results can be summarized af follows:

1. Activity of DNase I decreased and activities of DNase II and of a DNase I-inhibitor increased under the influence of high doses of folic acid. Significant effects were observed 16 — 24 hours after folic acid-injections. Extreme values (80% decrease [DNase I], 180% increase [DNase II, DNase I-inhibitor]) were reached after 2 and 4 days and were dose-dependent. Control values reappeared within 1 — 3 weeks.

2. Protein- and DNA-content of the thymus behaved very similarly to DNase I-activity of the kidney.

3. The increase of the DNase II-activity of the kidney under the influence of folic acid resulted from enzyme induction. As to the behaviour of DNase I loss of enzyme out of damaged cells and the induction of a DNase I-inhibitor in the kidney must be taken into account.

4. In many systems DNase I may control DNA-synthesis. Preliminary studies on the behaviour of folic acid-induced reaction of the kidney, when inhibited by X-irradiation, Actinomycin D, Actidione, or poly (vinylsulfate), suggest that DNase I-inhibitor plays a certain role in combining protein- and DNA-synthesis by inhibiting DNase I.
Stickstoffinduziertes Gitter beim Bor: I-tetragonales Bornitrid (B12)4B2N1–2 / The Nitrogen-Induced Lattice of Boron: I-Tetragonal Boron Nitride (B12)4B2N1_2
Authors: Amberger Eberhard , Schmidt Herbert
Published: February 2015

During the pyrolysis of gaseous BCl3 or BBr3 and H2 on boron nitride substrate at 1150 - 1600 °C under very clean conditions, boron is formed with the α- or β-rhombohedral lattice and the II-tetragonal lattice. These lattices disappear when molecular nitrogen is added to the gas. Then the I-tetragonal lattice of (B12)4B2Nx appears, in which x depends on the temperature (1< x < 2).
PH-Triazaphosphorine
Authors: Ebeling Joachim , Leva Marco Avitabile , Stary Herbert , Schmidpeter Alfred
Published: February 2015

Equimolar mixtures of a biguanide and a diphenylphosphonite on heating under reduced pressure split off 2 moles of phenol. As products cyclic phosphazanes 3 were to be expected. Instead they undergo a hydrogen shift from N to P to give 2-hydrogen-2-alkyl-4.6-diamino-1.3.5.2-triazaphosphorines (4). This is taken as evidence that a phosphazene π-bond may well become part of a cyclic delocalised system and thus contribute substantially more to stabilize the PH-tautomer than an isolated one.

Carbonyl compounds add readily to the PH-bond, CCl4 substitutes the hydrogen for chlorine, which in turn may be displaced by alkoxy and amino groups. 31P- and 1H-NMR data, especially the PH- and PD-coupling patterns sustain the assigned structures.
Substituent Effect on Reactivity of Alkyl Thiolacetates
Authors: Dutka F. , Márton A. F. , Vinkler P.
Published: February 2015

Kinetics of catalyzed acyl group exchange between acetic-1-14C anhydride and alkyl thiolacetates was investigated. The exchange is not accompanied by chemical reaction and demonstrates the full equivalency of anhydride acyl groups in the process. The rate of exchange is lowered by increasing branching rather than lengthening in S-alkyl substituents. The role of catalyst and structures of possible intermediates are interpreted. Upon existing linear structure-reactivity relationship a common mechanism involving sulfur atom as the reaction site seems to be operative.
Cyclodehydrohalogenation with Potassium Tertiary Butoxide in Dimethyl Sulfoxide
Authors: Chatterjee Basanta G. , Abdulla Riaz F. , Nyss Noel L.
Published: February 2015

Potassium tertiary butoxide in dimethyl sulfoxide solution has been shown to act as an efficient base in effecting the cyclo-dehydrohalogenation of halogen-acylamino-esters and -ketones. For certain specific cyclizations it is superior to the bases thus far used, yielding compounds of high purity in short reaction times. The first reported synthesis of a piperidinone by this route has been achieved.
Einfluß von 2-Desoxy-2.3-dehydro-N-acetylneuraminsäure auf Myxovirus-Neuraminidasen und die Replikation von Influenza- und Newcastle Disease Virus / Influence of 2-Deoxy-2,3-dehydro-N-acetylneuraminic Acid on Myxovirus-neuraminidases and the Replication of Influenza- and Newcastle Disease Virus
Authors: Meindl P. , Bodo G. , Lindner J. , Palese P.
Published: February 2015

Neuraminidase of Influenza-A-Melbourne virus was competitively inhibited by 2-deoxy-2,3-dehydro-N-acetylneuraminic acid. The inhibition constant (KI) was found to be 5.3 × 10-6 mol/l. The inhibition of different viral neuraminidases was found to vary considerably. The release of Influenza-A-Melbourne virus adsorbed to chick erythrocytes was strongly inhibited by 2-deoxy-2,3-dehydro-N-acetylneuraminic acid. This substance also influenced the replication of neuraminidase containing viruses. The extent of this inhibition was variable. In contrast, the replication of viruses not containing neuraminidase was not affected.
Rhythmic Incorporation of P32 and C14-uracil in Early Mitotic Cycles of Limnaea (Mollusc) Eggs
Authors: Brahmachary R. L. , Ghosal D. , Tapaswi P. K.
Published: February 2015

Incorporation of P32 and C14-uracil into RNase-sensitive, acid-insoluble fraction takes place in well defined cycles in course of the early cleavage in Limnaea embryos. This suggests a cyclic RNA synthesis. 40-50% less RNA is transcribed during the latter half of each cell division cycle. The rhythm is absent in the homogenate. The relevance of the findings has been discussed.
Sterische Wechselwirkungen im Innern cyclisdier Verbindungen, 19 / Steric Interactions of Inner Atoms in Cyclic Compounds, 191
Authors: Vögtle Fritz , Lichtenthaler Rainer
Published: February 2015

The synthesis of a series of new heterocyclic [3.3] metacyclophanes has been carried out. The 1H-NMR-spectra of the new compounds have been studied with regard to configurational problems and conformational mobility.
Über die thermische Denaturierung von trockener Ribonuclease /A Study of the Dry Thermal Denaturation of Ribonuclease
Authors: Schüssler Helga
Published: February 2015

The irreversible thermal denaturation of dry ribonuclease in the temperature range between 105 and 140°C is a complex process, leading to a very large number of derivatives, different in conformation, enzymatic activity, and amino acid composition. By gelfiltration three groups of molecules can be separated. Two of them having low enzymatic activity are composed of larger molecules than the native one. The third group retaining most of the enzymatic activity is composed of molecules nearly unchanged in molecular volume. These molecules apparently unaltered in gelfiltration experiment are definitely different from the native molecules, as can be shown by the different “melting curves” measured optically by UV-absorption at 287 nm in the temperature range between 20 and 70 °C. The heterogenity and the change in conformation was further demonstrated by ion exchange chromatography yielding several enzymatically active derivatives of ribonuclease. Amino acid analysis of heat denatured ribonuclease showed a loss of lysine and histidine. According to the rather complex process of denaturation the enzymatic activity does not decay during the heating time in an exponential way with a single time constant. Nevertheless during the first two hours of inactivation and especially at higher temperature the survival curves follow this pattern rather closely. From the slope of the survival curve an effective activation enthalpy of 23 kcal/mole and an activation entropy of -22 cal/mole · degree were obtained. Comparison between denaturation induced by heat and by ionizing radiation shows that similar types of damage occur at the molecular level.
Interactions Between Ferredoxin and Chlorophyll in a Monolayer System
Authors: Brody Seymour Steven
Published: February 2015

Ferredoxin (Fd) is surface active; both its area/molecule, A, and surface potential, ΔV, (at an air-water interface) vary with the pH of the subphase. From the surface isotherms (at pH 7.7) A and ΔV are 167 A2 and 170 ± 20 mV, respectively, when the surface tension is 10 dyne/cm.

Fd and chlorophyll a (Chl) appear to form a mixed monomolecular film. At pH 7.7 a maximum interaction between Fd and Chl is observed when the monolayer contains a mole ratio of Fd/Chl ≅ 2. Irradiaion of Chl-Fd films, in nitrogen atmosphere, results in a bleaching of Chl and an increase of ΔV. The quantum yield for this bleaching is estimated to be 0.4.
Freisetzung von 51Chrom aus markierten HeLa-Zellen nach Poliovirus-Infektion / Release of 51Chromium from Labeled HeLa-Cells after Infection by Poliovirus
Authors: Koschel Klaus
Published: February 2015

HeLa-cells labelled with 51Chromium start to release 51Cr into the medium 5-6 hours after infection with poliovirus. 51Cr-release is only observed when the viral genome is intact. Virus particles previously irradiated by UV do not cause chromium-release. Furthermore, protein synthesis must be allowed to proceed for 3-4 hours, p.i. for the effect to take place. Viral RNA synthesis is not required. Chromium release, release of viral particles and leakage of cellular proteins into the surrounding medium follow the same time course and have identical requirements. They are therefore considered to reflect a single phenomenon, a leakiness of the cell due to virus infection.
III. The Effect of Guanidine on Early Functions
Authors: Koschel Klaus , Wecker Eberhard
Published: February 2015

Guanidine does not inhibit the translation of viral RNA into virus specific proteins but it seems to prevent the generation of functional viral polymerase from precursor material. In the presence of guanidine, “inhibitory protein (s) ” responsible for the shut-off of cellular protein synthesis are still produced provided that the multiplicities of infection are high. The incoming (parental) viral RNA appears to be functional as messenger for only a limited number of translational cycles.
Der Einfluß von Licht auf die Eiablage des Copepoden Cyclops vicinus / The Influence of Light on the Egg-laying of the Copepod Cyclops vicinus
Authors: Spindler Klaus-Dieter
Published: February 2015

Cyclops vicinus shows a double-peaked rhythm of egg-laying under long-day-conditions with peaks in a distance of 12 hours. The rhythm of egg-laying is preserved after extirpation of the eyes and also after the passage of long-day-conditions to continuous illumination. The light-dark-cycle acts as a Zeitgeber, copulation is without effect on the rhythm.
Phosphinimino-phosphine durch Entsilylierung von N-Silyl-phosphiniminen / Phosphinimino-phosphines by Desilylation of N-silyl-phosphinimines
Authors: Wolfsberger Werner , Pickel Hans H. , Schmidbaur Hubert
Published: February 2015

Desilylation reactions of N-trimethylsilyl-trimethyl-phosphinimine (1) with PCl3 and CH3PCl2 lead to the formerly unknown phosphinimino-phosphines 2 and 3, which are characterized by elemental analysis, molecular weights, and 1H- and 31P-nmr spectra. The action of (CH3)2PCl on N-trimethylsilyl compounds does not afford the expected desilylated products (4, 6). Instead a second mole of (CH3) 2PCl is added immediately to yield the ionic species 5 and 7.
Über die Einschiebung von Metallen der II. Nebengruppe in die Metall-Metall-Bindung zweikerniger Carbonylmetallate / About the Insertion of Group II Metals into the Metal Metal Bond of Binuclear Carbonylmetalates
Authors: Behrens H. , Feilner H.-D. , Lindner E. , Uhlig D.
Published: February 2015

When [Cr2 (CO)10]2⊖ or [Fe2 (CO) 8]2⊖ is reacted with Hg i. e. with group II metals at long reaction times above 100 °C insertion of the named metals into the Cr-Cr i. e. Fe-Fe bond of the both carbonylmetalates occurs yielding the new anionic complexes [(OC) 5Cr- Hg- Cr (CO) 5]2⊖

i. e. [(OC) 4Fe-M-Fe (CO)4]2⊖ (M = Zn, Cd, Hg). The properties of the compounds as well as their IR and Raman spectra will be discussed.
Reaktionen an Diborylamin-Palladiumkomplexen / Reactions on Diborylamine Palladium Complexes
Authors: Schmid Günter , Weber Lothar
Published: February 2015

Bis [bis (dimethylamino) boryl] dibromobenzyl - amine - palladium - bromide C6H5C (Br2) - N {B [N (CH3)2]2}2PdBr and the corresponding iodo complex react with phosphines like (C6H5)3P or (C6H5)2P-CH2-CH2-P(C6H5)2 in benzene solution under substitution of the diborylamine ligand. Substitution products are {[(CeH5) 3P]2PdBr}2, [(CeH5) 2P (CH2)2 P (C6H5) 2PdBr] 2 and [(C6H5)2P(CH2)2P(CeH5)2PdJ]2, diamagnetic crystalline compounds. On the contrary the dimeric C6H5C(J2) - N{B[N(CH3)2]2}2PdJ and P(CeH5)3 form a complex with the formula C6H5C(J2)-N{B[N(CH3)2]2}2PdJ[P(C6H5)3]2. Here the diborylamine seems to be co ordinated only by one BN2-group. The other BN2-group of the starting material is substituted by the first, the co ordinated iodine atom of the Pd-J-Pd-bridge by the second phosphine molecule. A solution of this phosphine complex in CH2Cl2 leads to yellow crystals of [(CeH5) 3PPdJ] n.
Synthesis of rRNA, tRNA and Other RNA-species Concomitant with Polyribosome Formation in Aging Potato Tuber Slices
Authors: Kahl Günter
Published: February 2015

One of the earliest consequences of slicing plant storage organs such as potato tubers into thin disks is the formation of polysomes, which in potato slices is complete after 9 hours and is dependent on transcription. Fresh disks do not incorporate 32P, 3H-uridine or 14C-leucine into their ribosomes, whereas ribosomes and polysomes of aged disks use these precursors effectively. This development can be completely blocked by actinomycin D. Among the different RNAs synthesized during aging is 28S- and 16S—rRNA, 5S—RNA, tRNA, and a component sedimenting around 15—18S with a base-composition different from 16S—rRNA, 5S- and 4S—RNA and which supports peptide formation in an in vitro incorporation system.

It is suggested that this compound represents mRNA, which is not available immediately after slicing the tissue. These findings are consistent with the view of a derepression phenomenon in sliced storage tissue.
Activation of Protein Synthesis in Aging Potato Tuber Slices
Authors: Kahl Günter
Published: February 2015

Whereas ribosome preparations of freshly sliced potato disks do not show appreciable activity in an in-vitro amino acid incorporation system, aging of the tissue leads to a greatly enhanced incorporation activity which reaches its maximum 24 hours after slicing. If ribosomes from freshly excised disks are provided with polyuridylic acid, their activity in the incorporation of phenylalanine is increased about 8 fold.

Moreover, an RNA-fraction can be dissociated by EDTA from ribosomes of aged potato tuber slices, which sediments at 15 —18S, has a base composition different from that of 16S — rRNA, 5S-and 4S —RNA, and is not present on ribosomes of fresh slices. Its appearance is inhibited by actinomycin D and therefore most probably dependent on transcription. This compound, purified from sucrose gradients, enhances in vitro leucine incorporation into peptide material by ribosomes of fresh potato slices.

The possibility is discussed that this fraction-among other factors-is responsible for the enhanced protein synthesis after slicing plant storage organs, and is indicative of a general derepression phenomenon in these tissues.
Charge-Transfer Interactions of Aliphatic Amino Acids with Metal Ions
Authors: Lohmann Wolfgang
Published: February 2015

The effect of various non-SH-containing amino acids on an electron spin resonance spectrum as well as on an optical absorption spectrum of an aqueous copper (II) solution was investigated. The data obtained indicate that a charge-transfer complex is formed with amino acids acting as electron donors. A plot of the wavelength of the CT-band vs. the pK values of the carboxyl group exhibits a straight line with the larger pK values appearing at shorter wavelengths. Similar results were obtained when the intensity was plotted vs. the pK values of the amino group; again, higher pK values correspond to lower intensities. Thus, the method allows the determination of the pK values of prosthetic groups of amino acids. The data obtained are in good agreement with the CT-theory.
Die Reduktion von Tetrachlorkohlenstoff durch hydratisierte Elektronen, Η-Atome und reduzierende Radikale / The Reduction of Carbon Tetrachloride by Hydrated Electrons, H-Atoms, and Reducing Radicals
Authors: Köster R. , Asmus K.-D.
Published: February 2015

The reduction of carbon tetrachloride by hydrated electrons, H atoms and reducing radicals has been investigated by pulse radiolysis conductivity methods. It has been found that one Cl® ion is formed per reducing species. A chain reaction is observed in the γ-radiolysis of solutions of CCl4 and iso-propanol, diethylether, and tetrahydrofurane. Mechanisms and kinetic data are discussed.
Seltene Flavonoid-Aglykone im lipophilen Exkret von Alnus glutinosa / Rare Flavonoid-aglycones in the Lipophil Excretion of Alnus glutinosa
Authors: Wollenweber Eckhard , Bouillant Marie-Louise , Lebreton Philipp , Egger Kurt
Published: February 2015

The terpenoid excretion on buds of Alnus glutinosa is shown to contain free flavonoid aglycones. These are pectolinarigenine, centaureidin, the 3,6-dimethylether, 6,4′-dimethylether and 3,6,4′-trimethylether of 6-hydroxykaempferol and isorhamnetin.
Metallkomplexe mit paramagnetischen Salicylaldimin- und Thiosemicarbazon-Liganden / Metal Complexes of Paramagnetic Salicylaldimine and Thiosemicarbazone Ligands
Authors: Jahr Dieter , Schwarzhans Karl E. , Nöthe Dietrich , Burkert Paul K.
Published: February 2015

A series of complexes formed between metals and the stable free radicals 2,2,6,6-tetramethylpiperidine-1-oxyl-4- (N-salicylaldimine) and 2,2,6,6-tetramethylpiperidone (4) -1-oxyl-thiosemicarba-zone has been prepared. The magnetic moments and the epr spectra of the complexes have been investigated. Some of the complexes show a temperature dependent interaction between the radicalic nitroxyl groups of the ligands. No interaction was found, however, between the metal ion and the unpaired electrons of the ligands.
Über Alkali-Oxofluorometallate der Übergangsmetalle IV
Authors: Pausewang Gerhardt
Published: February 2015

The oxyfluorides A2NbOF5 and A,MoO2F4 (A = Rb, Cs, NH4) were prepared and investigated by x-rays. Rb2NbOF5 and Cs2NbOF5 crystallize hexagonally (K2GeF6-type); the compounds A2MoO2F4 and (NH4) 2NbOF5 show orthorhombic symmetry.
Optisch aktive Übergangsmetall-Komplexe, IX
Authors: Brunner Henri , Schindler Hans-Dieter
Published: February 2015

The enantiomeric complexes ( + ) - and ( - )-C5H5Mn(COOCH3) (NO)P(C6H5)3 were prepared, firstly by a transesterification of the diastereomeric menthyl derivates ( + )- and (-) -C5H5Mn (COOC10H19) (NO)P(C6H5)3, secondly by OCH3⊖-addition to the cations of ( + )-and (-) - [C5H5Mn (CO) (NO) P (C6H5)3] [PF6].

The kinetics of the exchange of triphenylphosphine in C5H5Mn (COOCH3) (NO) P(CeH5) 3 were investigated by deuteration and monitored by IR spectroscopy. The rate of this exchange in benzene solution is equal to the rate of racemisation of (+) - and (-)-C5H5Mn (COOCH3) (NO) P(C6H5)3 in the same solvent.

It is concluded that the rate determining step for the change in configuration at the asymmetric manganese atom is the dissociation of triphenylphosphine. In this reaction an achiral intermediate of relatively high stability is formed.
Massenspektren synthetischer methylen- und nicht-methylen-unterbrochener cis, cis-Oktadecadiensäure-methylester als Tetra-O-trimethylsilyläther / Mass Spectra of Synthetic Methylene- and Non-Methylene-Interrupted cis-cis-Methyl-Octadecadienoates as Their Tetra-O-Trimethylsilylether
Authors: Murawski Uwe , Egge Heinz , Zilliken Fritz
Published: February 2015

The 20-eV-Mass spectra of eight methylene- and eight non-methylene-interrupted cis,cis-methyl-octadecadienoates as their tetra-O-trimethylsilyl derivatives are given. The fragmentation pattern dependent on the original position of double bonds and number of methylene-groups between the two double bonds is discussed.
Tetrazolium-Bioautographie von Pteroylglutaminsäure-Konjugaten / Tetrazolium-Bioautography of Pteroylglutamic Acid Conjugates
Authors: Schlie Ilse , Jaenicke Lothar
Published: February 2015

A microbioautographic method for the identification of pteroylglutamic acid derivatives and their glutamyl conjugates is described. Chromatograms or pherograms of mixtures of the compounds are treated with chicken pancreas conjugase, followed by tetrazolium bioautography. This combined procedure allows qualitative and semi-quantitative analyses of folate compounds in biological material in the nano- and picomole range. Application of this method to extracts of different sources proved the following: (1) the presence of 10-formyl pteroyl-γ-heptaglutamate as the only folate derivative in yeast boiled juice; (2) Clostridium kluyverii and pastorianum contain almost exclulively pteroyl-γ-triglutamic acid; (3) the main folate activity in human leucocytes is 5-methyltetrahydropteroyl monoglutamate.
On the Biosynthesis of Juvenile Hormone in the Adult Cecropia Moth
Authors: Metzler Manfred , Dahm Karl Heinz , Meyer Dietrich , Röller Herbert
Published: February 2015

In adult males of the giant silk moth Hyalophora cecropia (L.) the amount of juvenile hormone (JH) extractable from the abdomens increases sharply between the first and fourth day of adult life; 4-8 day-old moths contain up to 6 μg. During the biosynthesis, L-methionine provides the ester methyl group of both JH and its lower homologue JH-II. It does not contribute to the formation of the carbon skeleton. Farnesol, farnesyl pyrophosphate, and propionate are not utilized. Mevalonate is extensively incorporated into trans,trans-farnesol, but not into the sesquiterpene-like hormone. This result indicates that JH is not synthesized via mevalonate in the adult moths. Label of 2-14C-acetate was recovered in both JH and farnesol; the incorporation rate, however, was very small. The label of JH was located in the carbon skeleton.
Identity of Streptolysin-O and NAD-Glycohydrolase (EC 3.2.2.5)
Authors: Fehrenbach Franz J.
Published: February 2015

The homogeneity of purified NAD-glycohydrolase (EC 3.2.2.5) from Group C streptococci was demonstrated by analytical ultracentrifugation, disc electrophoresis and immunochemical analysis. Together with earlier characterization procedures the data show that the enzyme is homogenous in molecular seize, molecular form and electrophoretic charge. In addition, the enzyme has been shown to possess strong hemolytic activity which could be activated by thiol compounds. It was concluded from the analytical data that NAD-glycohydrolase- and Streptolysin-O-activities are catalytic functions of one protein molecule. Therefore the lysis of red blood cells by Streptolysin-O may be regarded as an enzymatic process catalyzed by an NAD-glycohydrolase.
Untersuchungen über die Mischassoziation einiger Nucleosid-Derivate in Lösung / Investigations about Co-association of some Nucleoside-derivatives in Solution
Authors: Breuer H. , Perkampus H.-H.
Published: February 2015

The co-assoziation of four nucleoside-derivatives was investigated using NMR spectroscopy. It turned out that the constant of co-association is at least ten times as great as the value for selfassoziation it a Watson-Crick pair was used. Thermodynamic data were calculated from the temperature dependence of the assoziation constant.
Aluminium Derivatives of Tridentate Bifunctional Schiff Bases Derived from Salicylaldehyde and Benzoylacetone
Authors: Dayal J. , Mehrotra R. C.
Published: February 2015

S = salicylaldehyde and benzoylacetone and B = (CH2-)2, -CH2-CH -CH3 and C6H5) in different stoichiometric ratios have been synthesised. The products Al (OPri) (SB) are soluble in benzene. The tertiary butoxy products have been prepared by the alcohol interchange technique. Infrared spectra of the new derivatives are reported. Thermogravimetric analyses have also been carried out.
Metal Ions and Hydrogen Peroxide. XXV
Authors: Waldmeier Peter , Prijs Bernhard , Sigel Helmut
Published: February 2015

The decomposition of H2O2, catalyzed by the Co2® complex of 4,4′,4″,4″′-tetrasulfophthalocyanine (CoIIPTS), was investigated in the pH range 3.8 through 10 by measuring the initial rate, v0=d(O2)/dt, of the increasing formation of O2 (25°; I=0.1). In this pH range v0 is proportional to the initial concentration of H2O2 (determined at pH 5.0 and 9.2). Due to the dimerization (log KD=5.47 ±0.09 at natural ionic strength and about 7.63 ±0.16 in 0.1 M NaClO4; 25°) and polymerization of CoIIPTS the catalyst and its reaction order are difficult to establish: Based on the experimental evidence it is suggested that v0 is proportional to the concentration of monomer CoIIPTS. Additionally, there is evidence that the experimentally determined v0 contains the contributions of a pH-independent and a pH-dependent reaction course. These results are analog to those obtained earlier with FeIIIPTS as catalyst. A mechanism for the catalyzed disproportionation of H2O2 by CoIIPTS is proposed. The catalase-like activity of CoIIIPTS (OH) is smaller than that of CoIIPTS and the pH-dependence is different.
Untersuchung von Calciumisotopieeffekten bei heterogenen Austauschgleichgewichten / Investigation of Isotopic Effects of Calcium in Heterogeneous Exchange Equilibria
Authors: Heumann Klaus Gustav , Lieser Karl Heinrich
Published: February 2015

The following heterogeneous exchange equilibria have been examined for isotopic effects: CaCO3/Ca(aq.)
2⊕. Ca-GBHA/Ca(aq.)
2⊕ and Ca(Dowex 50)
2⊕/Ca(aq.)
2⊕ (GBHA = glyoxal-bis (2-hydroxyanil)). The isotopic ratios 44Ca/40Ca and 48Ca/40Ca were determined by means of a mass spectrometer with a thermal ion source. In the system CaCO3/Ca(aq.)
2⊕, the elementary separation factor was found to be less than 1‰ or 0,5‰ per mass unit, respectively.

For the exchange in the system Ca-GBHA/Ca(aq.)
2⊕ in the concentration range from 0.011 to 0.84 M an elementary separation factor less than 1‰ per mass unit was found; from a three-stage experiment at a calcium concentration of 1.23 M it was concluded that the elementary isotopic effect is less than 0.4‰ per mass unit. Therefore no isotopic fractionation is to be expected for precipitation of inorganic or organic calcium salts.

An enrichment of the heavier calcium isotopes in the solution was found in the case of the exchange in a Dowex 50-X12 loaded column. The isotopic effect depends on the concentration of the hydrochloric acid used as the eluent.
1H-, 13C- und 31P-KMR-Spektren einiger ditertiärer Phosphine / 1H-, 13C- and 31P-NMR Spectra of Some Ditertiary Phosphines
Authors: Marsmann Heinrich , Horn Hans-Georg
Published: February 2015

13C- and 31P-NMR data of some ditertiary phosphines are given and 1H-NMR spectra of these compounds in different solvents are discussed.
Quantitative Structure-Activity Studies of Hydrazones, Uncouplers of Oxidative Phosphorylation
Authors: Draber W. , Büchel K. H. , Schäfer G.
Published: February 2015

α-Acyl-α-cyanocarbonyl-phenylhydrazones are effective uncouplers of oxidative phosphorylation. The pl50-values of a series of 60 hydrazones with substituent variations in six positions of the molecule were determined in rat liver mitochondria. They ranged from 4.96 to 7.06. The biological data together with physico-chemical compound and substituent parameters were analysed by multiple regression techniques to establish the structure activity relationship.

The integral parameters pKa and log P (partition coefficient) gave correlations of only moderate significance. Good agreement of found and calculated pl50-values was obtained by an equation with electronic (σ) and hydrophobic (π) substituent parameters in linear and quadratic terms. It is concluded that the contribution of a substituent to uncoupling activity depends on its position in the molecule. The activity is enhanced by hydrophobic shielding of the acidic NH-group. The relevancy of these results in relation to current theories on the mechanism of oxidative phosphorylation is discussed.
Über Teilreaktionen der Photosynthetischen Sulfatreduktion in zellfreien Systemen aus Spinatchloroplasten und Chlorella / Enzyme Reactions Involved in Photosynthetic Sulfate-Reduction in Cell-free Systems of Spinach Chloroplasts and Chlorella
Authors: Schmidt Ahlert
Published: February 2015

Cellfree extracts from Chlorella, spinach leaves or spinach chloroplasts convert radioactive sulfate into a S-sulfocompound already in the dark. The reaction requires ATP, Mg2⊕ ions and compounds with SH groups. The later are needed for activation of the enzym and as substrates and acceptors for the sulfogroup. The compound formed if glutathion is used has been identified as S-sulfoglutathion. Other products formed from sulfate and ATP in the dark by spinach or chlorella extracts are APS and PAPS. The formation of PAPS requires the presence of a SH-group. Both cellfree extracts transfer the sulfate group from APS and PAPS onto glutathion to form S-sulfoglutathion. No ATP is needed in this reaction, neither with PAPS nor with APS as substrate.
Pteridine and Riboflavin in Tumor Tissue and the Effect of Chloramphenicol and Isoxanthopterin
Authors: Kokolis N. , Mylonas N. , Ziegler I.
Published: February 2015

Human squamous cell carcinoma has elevated levels of tetrahydrobiopterin. As the level of riboflavin is low, the ratio tetrahydrobiopterin/riboflavin shows values of 5 - 8.3. In contrast, in differentiated tissues with high metabolic activity but low mitotic rate, like submaxillary glands, elevated levels of tetrahydrobiopterin are accompanied by high content of riboflavin. Thus the ratio tetrahydrobiopterin/riboflavin in kept as low as about 0.5. Chloramphenicol and, in particular, isoxanthopterin reduce tumor growth in rats and prevent tetrahydrobiopterin accumulation as well.
Über Erdalkalimetall-Oxocuprate. VI.
Authors: Teske Chr. L. , Müller-Buschbaum Hk.
Published: February 2015

The preparation and chemical properties of barium-oxocuprat (I) inclusive the results of the crystal structure determination by single crystal X-ray investigations are described. BaCu2O2 crystallizes isotypically with SrCu2O2 . (a = 5.72 and c = 10.06 Å. Spacegroup : D19
4h - 141/amd.) The influence of the bigger Ba2⨁-ion on the oxigenconfiguration surrounding the cations is discussed. It seems that the stretched O - Cu - O-dumbell is an invariable structural element in the oxocompounds of copper (I), which is shown by comparison of already known oxocuprates (I) . Only the way of interchainment varies evidently with stoichiometry.
Metalltrifluorphosphin-Komplexe, XXX / Metal-Trifluorophosphine Complexes, XXX
Authors: Kruck Thomas , Krause Volker
Published: February 2015

The title compound, CpMn (PF3) 3, is formed by photochemically induced CO/PF3 exchange with CpMn (CO)3 in a THF-solution. The yellow crystalline solid is obtained in 70% yield. It is obvious that in the course of this reaction intermediate THF-substitution-products are formed. For the first time we were able to prove that besides CpMn (CO) 2THF, CpMn (THF) 2CO is also a product of the above reaction. These intermediate THF-complexes are already at normal pressure able to exchange THF for PF3.
Über den Einfluß langkettiger ungesättigter Fettsäurereste auf die Kinkenbildung in Membranmodellen / Influence of Unsaturated Long Chain Compounds on Kink Formation in Membrane Models
Authors: Weiss Armin , Spiess J. , Stuke E. , Lagaly G.
Published: February 2015

In connection with the permeation theory of Träuble, in which kinks are considered as carriers through lipid layers of membranes, the influence of unsaturated long chain compounds on the kink structure is studied in membrane models.

Unsaturated compounds in bimolecular films of saturated long chain compounds lead to higher kink concentrations and favor the random distribution of the kinks.
31P-NMR-Spektren von Phosphor(V)-nitrid-chloriden und Phosphor(V)-Schwefel(VI)-nitrid-chloriden / 31P NMR Spectra of Phosphorus (V)-nitride-chlorides and Phosphorus (V)-sulfur (VI)-nitride-chlorides
Authors: Haubold Wolfgang , Fluck Ekkehard
Published: February 2015

Preparation and properties of linear and branched phosphorus nitride chlorides with chlorosulfurylimide endgroups are described.

The nmr spectra of phosphorus (V) nitride chlorides and phosphorus (V) sulfur (VI) nitride chlorides are compared and discussed. Chemical shifts δ31p and δ19F , structure of resonance signals and coupling constants are tabulated.
Mechanism of Oxidation of some Aliphatic Aldehydes by Chloramine-T
Authors: Agrawal M. C. , Mushran S. P.
Published: February 2015

Kinetic studies on the oxidation of acetaldehyde, propionaldehyde, n- and iso-butyraldehyde have been made using chloramine-T as an oxidising agent in an alkaline medium. The reactions followed almost identical kinetics being first order with respect to both aldehyde and chloramine-T. The order with respect to alkali has been found to be almost equal to unity (0.8 to 0.90). Effect of an increase in the ionic strength was negligible while that of the addition of ethyl alcohol was negative. A mechanism involving the interaction of the enol anion of the aldehyde with chloramine-T best fits the kinetics data. Other possibilities have also been examined. Corresponding acids were found to be the oxidation products.
Nachweis und Bestimmung eines Hyaluronat-Protein-Komplexes in der Peritonealflüssigkeit von Ratten nach Injektion von Phytohämagglutinin / Occurence and Estimation of a Hyaluronate Protein Complex in the Peritoneal Fluid of Rats after Injection of Phytohemagglutinin
Authors: Greiling H. , Mohr W. , Beneke G.
Published: February 2015

In the peritoneal fluid of rats hyaluronate is produced after intraperitoneal injection of phytohemagglutinin.

The hyaluronate concentration was quantitated spectrophotometrically after enzymatic degradation by hyaluronatlyase and a maximum amount of 90 mg% hyaluronate was found after intraperitoneal injection. The production of hyaluronate after phytohemagglutinin injection is dependent on the time and concentration of the phytohemagglutinin. Maximum hyaluronate synthesis is about 48 h after phytohemagglutinin, after this time the hyaluronate concentration is decreased.

After phytohemagglutinin stimulation we isolated a hyaluronate protein complex from the peritoneal fluid by cetylpyridinium chloride precipitation followed by chromatography on Biogel P-150. The dominating amino acids were aspartic acid and glutamic acid.
Reaktion von Arsen-Sauerstoff-Verbindungen mit überkritischem Ammoniak Kristalldaten von Ammoniummetaarsenit NH4AsO2 / Reaction between Arsenic-Oxygen-Compounds and Ammonia above the Critical Point Crystal Data of Ammoniummetaarsenite NH4AsO2
Authors: Jander Jochen , Stoecklein Wilfried
Published: February 2015

The reactions between As2O3, As2O5, As(OC2H5)3, and NH3 above the critical point up to 3700 atm were investigated and described. The reaction products formed under various pressure and temperature conditions are compounds with arsenic-nitrogen bondings and ammonium salts of different arsenic acids. The lattice constants and the space group of NH4AsO2 produced by the reaction of As2O5 and NH3 under ammonothermal conditions were determined.
Brom-cyclobutadien-eisentricarbonyl / Bromo-cyclobutadiene-irontricarbonyl
Authors: Brune H. A. , Horlbeck G. , Röttele H.
Published: February 2015

The synthesis of bromo-cyclobutadiene-irontricarbonyl is reported and compared with a former attempt of synthesis that yielded another product. Spectra are discussed with respect to structure and bonding properties.
Über substituierte Pentaphenyl-cyclopentadienyl-Verbindungen und Tetracyclone, IX.
Authors: Grunder Hans-Theodor , Haink Hans-Jochen , Kurreck Harry , Richter Wolf Jürgen , Woggon Wolf-Dietrich
Published: February 2015

A linear relationship has been found by correlating simple HMO- and McLachlan- HMO-spin densities with g-values of substituted tetraphenylcyclopentadienone (tetracyclone) metal ketyls, measured by EPR techniques. Assuming an out-of-plane angle — referred to the plane of the cyclopentadienone — of 60° for the α- and 30° for the β-phenyls the EPR data can be explained satisfactorily. This model serves as well to characterize, by means of HMO calculation, the two vis. bands of tetracyclone compounds (which are dependent on the nature of substituent) to be intramolecular charge transfer bands.
On the Biosynthesis of the Benzimidazole Bases Occurring in Corrinoids
Authors: Renz Paul , Bauer-David Andrée J.
Published: February 2015

A hypothesis by Bernhauer on the biosynthesis of the benzimidazole bases of corrinoids implicates the possible existence of a corrinoid containing 6′,7′-dimethylnaphtho- (2′,3′) -imidazole-4,5 (DMNIA). In order to facilitate the detection of this corrinoid in natural sources by means of a reference compound, DMNIA was synthesized and added to cultures of Propionibacterium shermanii. Thus the new vitamin B12-analog DMNIA-cobamide was formed. The DMNIA-cobamide was degraded and its base isolated. This base had the same UV-spectrum and electrophoretic behaviour as the product prepared by chemical synthesis. On degradation of DMNIA-cobamide with cerous hydroxide DMNIA-α-D-ribofuranoside is formed. Perchloric acid treatment of DMNIA-cobamide yields DMNIA-α-D-ribofuranoside 3′-phosphate. The microbiological activity of DMNIA-cobamide cyanide tested with the vitamin B,12-requiring Lactobacillus leichmannii ATCC 7830 was equal to the activity of vitamin B12, with the Escherichia coli-mutant 113-3 it exhibited about 50% of the growth-activity of vitamin B12.

DMNIA-cobamide coenzyme shows approximately 10% of the coenzymatic activity of coenzyme B12 in the propanediol dehydrase reaction.
High Protective Action against Gamma Radiation Damage, by a Tryptophan-ethanol Mixture
Authors: Sánchez G. , Hasbún S. , Díaz E. , Grez M. , Lyon F. , Pieber M. , Romero C. , tohá J. C.
Published: February 2015

Between a group of non sulphydryl radioprotectors (methanol, formaldehyde, acetaldehyde, formiate, acetate, ethanol and tryptophan); ethanol and tryptophan were selected because its high protector action on irradiated purine and pyrimidine bases. At molarities of the order of 10—4 for tryptophan-ethanol and bases and DNA the respective DRF values were: for guanine: 20.58; for adenine: 3.75; for thymine: 4.94; for cytosine: 5.52; for uracil: 5.43; and for DNA: 18.95. For irradiated seeds protected with tryptophan-ethanol (1.5 × 10—3M; 2.6 × 10—2 M) the DRF value was of 3.33 and radiation damage becames evident only after a total dose of 2 × 104 rads.

A partial different mechanisms for radioprotection with ethanol and tryptophan is postulated; this is supported by the fact that when tryptophan molarities attains that of protected DNA, there are a rapid increase in its values of DRF, crossing up the ethanol protection curve.

Actually tryptophan could act not only as a radical scavenger, but also, as localized radical quenchor and/or energy trapper.
Blut-Hirn-Schranke und Placentar-Schranke für H-Thymidin und H-Cytidin bei der Maus / Blood-Brain-Barrier and Placental-Barrier for H-Thymidine and H-Cytidine in the Mouse
Authors: Schultze B. , Hörning N. , Maurer W.
Published: February 2015

The distribution in the organism of the mouse of free 3H-thymidine and 3H-cytidine was studied 1, 2½, 5 and 15 minutes after intravenous injection into normal and pregnant mice (20th day) using whole body autoradiography. The grain density measured over brain and fetus is 10 times smaller as compared to other tissues of the organism. This means that a blood brain barrier and placental barrier for thymidine and cytidine exists.
Binding of a Polycyclic Hydrocarbon to Mouse Skin Proteins
Authors: Diringer Heino , Weber Lutz
Published: February 2015

The tritium content of the L- and K-region of commercial available tritiated 1,2,5,6-Dibenzanthracene was measured and compared with the 3H-release after binding of the compound to mouse skin proteins. The results exclude an addition reaction to the K- and L-region and favour a substitution reaction at one C-atom.
Stimulierung von Kulturen embryonaler Rattenzellen durch Kälberserum / Stimulation of Embryonic Rat Cells in Culture by Calf Serum
Authors: Grimm Johanna , Frank Werner
Published: February 2015

Embryonic rat cells cultured in a synthetic medium are stopped in G1 phase if serum is omitted from the culture medium. On addition of calf serum these cells resume DNA synthesis after a lag phase of 15—20 hours. In the present paper the events concerning the metabolism of adenosine phosphates after stimulation by serum have been examined. The results are the following:

1. The concentration of cAMP in cells which have been incubated for 24 hours in serum-free medium is 32 times higher than that in cells growing in medium containing 10 per cent calf serum; the accumulated cAMP is metabolized within 10 min after the addition of 10 per cent calf serum. This has been confirmed by a double labelling technique after preincubation with radioactive adenosine as well as by estimation of cAMP using a protein-binding assay.

2. A cAMP-specific phosphodiesterase is activated shortly after stimulation; the enzyme activity in dialysed cell homogenates is increased within 30 min by a factor of 2.

3. Cells incubated in serum-free and those in serum-containing medium have equal amounts of ATP. On addition of serum the ATP concentration in cells preincubated in serum-free medium decreases by 27%; the original level is restored 20—30 min later.
ESR-Parameter und Bindungseigenschaften der Liganden in [Fe(NO)2(EZ3)X]-Komplexen/ESR Parameter and Bonding Properties of Ligands in [Fe (NO)2 (EZ3) X] Complexes
Authors: Schmidt Jörn
Published: February 2015

Isotropic g factors and hyperfine coupling constants of a series of complexes [Fe (NO) 2 (EZ3) X] are reported. In accord with theoretical suggestions, the g factors arrange the ligands EZ3 corresponding to their π acceptor abilities. Both donor and acceptor properties of the ligands exhibit considerable influence on the spin densities.
Reaktionen von Schwefel- und Phosphoramiden mit Trichlormethansulfenylchlorid / Reactions of Sulfur- and Phosphorus Amides with Trichloromethanesulfenyl Chloride
Authors: Roesky Herbert W. , Schafer Wolgang , Tutkunkardes Senol
Published: February 2015

Substituted amides react with tridiloromethanesulfenyl chloride in the presence of triethylamine to following compounds: S=PCl2NCH3SCCl3, S=PFCl2NCH3SCCl3, S =PFClNCH3SCCl3, S=PF2NCH3SCCl3, O = PCl2NCH3SCCl3, O= PFClNCH3SCCl3, O = PF2NCH3SCCl3, FSO2NCH3SCCl3 and CF3SO2-NCH3SCCl3. The properties of these substances are described. They were characteriszed by elemental analyses, IR- and mass spectra. 19F-, 1H- and 31P-NMR spectra are reported and discussed.