Volume 27, Issue 4

Homogeneous reaction systems showing automatic dropping-down behaviour have become known only recently. A synopsis of the so far devised basic circuits (i. e. prototype reaction systems) is presented. It is observed that the abstract design of these systems follows especially simple rules: They can be composed after the building-block principle from simpler flipping-systems. This is in accordance with the mathematical theory of these systems. An eventual technological significance of the presented class of chemical systems seems possible.

Fe (PF 3 ) 5 reacts with halogens to yield the dihalogeno-tetrakis (trifluorophosphine) -iron complexes X 2 Fe (PF 3 ) 4 (X = Cl, Br, J). The structure of the volatile cristalline compounds is octahedral with the halogen atoms in cis-position. The IR-, Mass- and F-NMR-spectra are reported and discussed; the Mössbauer-spectra are listed.

It is shown from infra-red measurements on the compound CoCl 3 (NH 3 ) 3 reported by WERNER that the complex contains bridging μ-chloro ions. Spectrophotometric measurements indicate cisposition of the μ-chloro ligands. Corresponding polynuclear μ-chloro complexes with trans-position of the μ-chloro ligands have been obtained reacting trans- [Co (N 3 ) 3 (NH 3 ) 3 ] or trans- [Co (CCl 3 CO 2 ) 3 (NH 3 ) 3 ] with concentrated hydrochlorid acid. A similar product has been obtained from solutions of trans- [CoCl 2 H 2 O (NH 3 ) 3 ] in conc. H 2 SO 4 adding conc. HCl.

The stability constants of the binary Cu 2+ complexes of glycine amide, diglycine, diglycine amide, triglycine, and tetraglycine were determined, as were those of the mixed-ligand Cu 2+ systems containing 2,2′-bipyridyl and one of the mentioned oligoglycines. The results evidence that all these complexes have the same structure and, therefore, the binding sites of the ligands have to be the terminal amino group and the oxygen of the neighbored amide group. The stability differences between the ternary and the binary complexes are in agreement with this interpretation. It is of interest to note that these ternary complexes are significantly more stable than expected on statistical reasons. With increasing pH, the amide groups in the binary complexes are successively deprotonated. Thus, with tetraglycine finally all three amide protons are displaced, and the amide nitrogens are bound to the square-planar coordination sphere of Cu 2+ . As in the Cu 2+ -2,2′-bipyridyl 1 : 1 complex, only two coordination positions are left for the binding of the oligoglycine, in the tenary complexes, only one amide group can be deprotonated. An increase in pH with deprotonation of other amide groups leads to a displacement of 2,2′-bipyridyl, i. e. the simple binary complexes result. No evidence could be observed for the coordination of a deprotonated amide group to an apical position of the coordination sphere of Cu 2+ . Additionally, while the displacement of the first amide proton in the several binary Cu 2+ oligoglycine complexes occurs over a large pH range (4 to 7), the deprotonation in all the mixed-ligand complexes takes place at pH approximately 8.

The synthesis of new coordination compounds of platinum crystallizing in a columnar structure is described. The reaction conditions leading to linear metal chains can be deduced by means of a simple charge transfer model.

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 δ 31 p and δ 19 F , structure of resonance signals and coupling constants are tabulated.

The crystal structure of (CH 3 NH 3 ) 4 InCl 7 has been determined by x-ray diffraction. The compound crystallises in the monoclinic space group C 2h 4 — P 2 / c with α=16.113 (3), b= 7.466 (5), c=20.300 (8) Å, β=127.9 (4)°, Z=4. A total of 834 independent reflections was used in solving the structure, which was refined to a conventional RI-factor of 0.076. The salt consists of InCl 6 3⊖ -respectively Cl ⊖ -anions and (CH 3 NH 3 ) ⊕ -cations.

Amber samples of different provenance have been investigated by electron impact and fieldionisation mass-spectrometry. Whereas electron-impact mass-spectra are not specific enough, fieldionisation spectra enable one to identify amber from Baltic-, Sicilian-, Canadian- and Libanese areas. Fe, Na, B, Ca, Mn, Al, Ti, Cu, Cr, V and Si could be determined by emission spectroscopy. Baltic amber shows a smaller trace-element content than all other samples investigated. Canadian amber shows a higher manganese content.

A study of the complexation reactions of dialkyltin dichloride with catechol has been carried out by potentiometric method and the correctness of the observed formation of 1:1 complex has been confirmed by preparative studies both in aqueous and non-aqueous media.

The photochemical synthesis of the title compounds is described. It has been established by spectroscopic evidence and by the x-ray structure of pinocarvone tricarbonyliron that in all these cases bonding to the iron involves only the π-system of the α,β-unsaturated ketones and not the nonbonding electrons of the keto group. The preferential site of monodentate coordination of α,β-unsaturated carbonyl compounds to transition metals is discussed on the basis of MO-considerations which are extended to 1,2-dicarbonyl compounds.

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.

A number of naphthalides in which the central carbon (C*) atom is attached to different rings obtained by condensation of phenols with 3-benzoyl-2-naphthoic acid are described. The constitution of the dyes has been studied and the visible UV and IR spectra have been presented and discussed. The absorption maxima of the dyes have been found to be shifted like those of phthaleins.

For the barnacle photoreceptors it is estimated that at 20°C a half-maximal flash response requires the photic activation of 1% of the tubulous microvilli. The decrease of photo-electric efficiency at high intensities and low temperature is attributed to less efficient 2 quantum activation of microvilli. The estimate of the light induced charge flux yields evidence for ionic depletion in an extracellular space which is restricted by glia cells. The integration of the current during the transient of the response to steps of intense light yields limits for the extracellular volume which are in accord with electron microscopic results. The observed reaction scheme with a ratio of latency time : duration of response : adaptation time independent of temperatur and type of photoreceptor is in a model explained with the same transfer processes occuring in volume elements of different size. A brief review of photoreceptors of other animals shows that in spite of different durations of the responses the reaction scheme of flash responses and the photo-electric efficiency (≈ 10 5 ions per absorbed photon) are similar for different photoreceptors.

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.

Experiments were undertaken to study the effect of introducing isolated mammalian cell mitochondria into tissue culture cells. The DNA of isolated mitochondria was labeled in vitro with 3 H-thymidine. Incorporation of 3 H-thymidine into mitochondrial DNA was increased tenfold by the addition of bovine serum albumin and sucrose to the assay. Labeled HeLa cell mitochondria were fused with WI38 (human fibroblast) and I-T-22 (Bromodeoxyuridine resistant mouse cell line) cells in the presence of Sendai virus and autoradiographs were made. The results indicated that isolated mitochondria may have been introduced into the cells by the fusion process. Fusion of mitochondria isolated from mouse tumor cell lines with isogenic primary mouse embryo fibroblasts induced permanent growth of these cells in tissue culture, whereas isolated mitochondria of mouse embryo fibroblasts or allogenic tumor cells did not have this effect.

Acid phosphatase and 5′-nucleotidase activity, present in fowl plague virus preparations, is separated from virus particles by a two-step sucrose gradient centrifugation. These enzymes may therefore be used to define the degree of purity of myxovirus preparations. ATPase activity, however, was found to be associated with virions of fowl plague.

The position of acidic, basic and phenolic amino acid residues of nucleoproteins and proteins of the TMV strains vulgare (and mutants of vulgare), dahlemense, and U 2 were determined by comparative potentiometric and spectrophotometric titrations in order to obtain more precise information about the interactions of proteins. In the nucleoproteins of all these mutants only 8 carboxylgroups of 16 (vulgare, A 14, Ni 1927 and U 2) and 8 of 15 (flavum, Ni 116, Ni 109 and Ni 606) can be titrated. Thus it is concluded that only these 8 groups are situated near the surface. The differences in the titration curves, measured at I=0.1 and I=0.02 show that one amino acid with pK 5.2 is titrated in vulgare but not flavum, Ni 116 and Ni 606. The titration curves of the mutant proteins differ from one another and from that of vulgare between pH 7 and 6 and this is probably due to aggregation which starts for each protein at different pH values. In addition, the differences in titration curves at pH values 4.5 are probably due structural changes. Also the titration curves of the strain proteins of vulgare, dahlemense and U 2 are different. The first binding of protons during the titration of the proteins occurs before pH 7 for U 2, about pH 7 for vulgare, and at pH 6.6 for dahlemense. Opalescence and sedimentation values indicate that aggregation takes place in the same sequence. At pH values >5 vulgare protein binds more protons than dahlemense and fewer than U 2. Due to the isoelectric state the U 2 protein precipitates at pH 5.5 (nucleoprotein at pH 4.1), dahlemense protein does not precipitate (although nucleoprotein does precipitate at pH 3.15) and the vulgare nucleoprotein and protein precipitate at pH 3.9. Spectrophotometric titrations indicate that two of 4 tyrosine residues are ionized in vulgare and mutant nucleoproteins (except Ni 2068 where 1.2 of 3 tyrosine residues are ionized). The dissociation of the first proton of a tyrosine residue begins with the depolymerization of the nucleoprotein which is not completed until the titration end point is reached (pH 12.6). The ionization of the tyrosine residues begins at lower pH values in proteins than in nucleoproteins and, furthermore, the protein contains an additional ionized tyrosine residue. In the nucleoprotein and protein of U 2 4.2 of 6 tyrosine residues are titrated whereas in dahlemense 2.3 and 3.8 tyrosine residues are titrated in nucleoprotein and protein, respectively. Binding studies with labelled lead ions show that vulgare, related mutants, and U 2 bind two lead ions per subunit whereas dahlemense binds 2.5. The comparison of all results shows that a constant number of acidic amino acid residues must be on the surface of the TMV particle in order to obtain a stable TMV nucleoprotein. Furthermore, two intermolecular interactions between carboxyl-carboxylate groups must be present for the aggregation of proteins to occur.

Photosystem I related phosphorylation of isolated chloroplasts was investigated with special reference to the stoichiometry between ATP production and electron transprt (ATP: 2e ⊖ ). The system studied contained DCMU to inhibit electron flow from photosystem II, ascorbate and DPIP to supply electrons to photosystem I, and methylviologen as electron acceptor. The following results were obtained: 1. Basal electron transport is stimulated by the addition of the phosphorylating system, indicating that phosphorylation is really coupled to non-cyclic electron flow. The ratio ATP: 2e ⊖ is 1, when the increase of electron flow obtained by the addition of ADP and phosphate is correlated to phosphorylation. This ratio is constant upon varying several parameters including DPIP concentration and light intensity. 2. In the absence of methylviologen a DPIP catalyzed cyclic phosphorylation takes place (cf. I. c. 7, 11, 12 ). Phosphorylation is not increased by the addition of methylviologen, indicating that both, the cyclic DPIP mediated and the non-cyclic system are coupled to the same phosphorylation site and limited by the same reaction step. 3. In the absence of oxygen a methylviologen supported cyclic phosphorylation occurs. Comparing optimum rates, phosphorylation under these conditions is about twice as high as in the noncyclic system. Therefore we conclude that two phosphorylation sites are involved in methylviologen catalyzed cyclic electron transport. This system is sensitive against trypsin treatment of the chloroplasts, whereas the linear system is not. 4. The two cyclic systems as well as the non-cyclic system are coupled to reversible proton uptake. Furthermore the linear system exhibits an irreversible uptake of hydrogen ions, which is stoichiometric to electron flow. From the reversible and the irreversible components of the pH changes the ratio of the proton pump to electron transprt can be calculated. Under steady state conditions the ration H ⨁ : e ⊖ approaches 1.

A novel law of mortality, discovered by the author, is compared with the Gompertz’s law with special regard to deviations (from the observed data), which turn out to be three times larger in the case of the Gompertz’s law.