Structural and spectroscopic studies of silylated cyclo- and bicyclosilanes

A number of cyclo-and bicyclosilanes have been prepared and structurally characterized by X-ray crystallography and Raman spectroscopy. 1,1,4,4- and 1,1,3,3-tetrakis(trimethylsilyl)octamethylcyclohexasilanes were found to exhibit unusual twist- and twisted boat-conformations. The UV absorption properties of all compounds were studied and found to show absorption maxima red shifted compared to the parent compound dodecamethylcyclohexasilane. Dedicated to Prof. Mitsuo Kira on the occasion of his reception of the Wacker Silicon Award 2005 and in recongnition of his numerous outstanding achievements in organosilicon chemistry.     

Beiträge zur Chemie der Pyrrolpigmente, 31. Mitt.: Die Spin-Gitter-Relaxation in den1H-NMR-Spektren von Bilatrienen-abc

The¹H-NMR spin lattice relaxation times of aetiobiliverdin-IV- and biliverdindimethylester were determined using the inversion recovery technique. The relaxation times of protons attached to the terminal rings A and D are longer than those situated at the rings B and C which points to a higher mobility of rings A and D. Moreover these measurements allowed an independent assignment of the¹H-NMR-signals of the methyl groups of biliverdindimethylester.

30. Mitt.:H. Falk undT. Schlederer, Ann. Chem., im Druck.     

A new approach to β-amino acids: biotransformation of N-protected β-amino nitriles

A number of novel N-protected β-amino nitriles were prepared as substrates for two nitrile-converting microorganisms, Rhodococcus sp. R312 and Rhodococcus erythropolis NCIMB 11540. The respective biotransformation products, β-amino acids, are known to be pharmacological very potent compounds.     

Beiträge zur Chemie der Pyrrolpigmente, 38. Mitt.: Zur Assoziation von Gallenpigmenten

The long standing problem of solvent dependent absorption spectra of certain bile pigments such as bilirubindimethylester has been solved by measurement of molecular masses by means of vapour pressure osmometry. Using this method and the investigation of the concentration and temperature dependence of the absorption spectra on several model compounds an association equilibrium for pigments of the rubinoid structural type could be confirmed. Moreover the optical properties of the coexisting species and the corresponding equilibrium constants could be deduced by spectroscopic techniques. Verdinoid pigments lacking free carboxylic functions on the other hand tend to be monomeric in solution. A heteroassociated species involving equimolar amounts of a verdinoid and a rubinoid pigment could be verified existing on adsorbents like silicagel.

37. Mitt.:Falk, H., Thirring, K., Tetrahedron, im Druck.     

Synthesis and microbial transformation of β-amino nitriles

Rhodococcus equi A4, Rhodococcus erythropolis NCIMB 11540 and Rhodococcus sp. R312 were investigated towards their ability to produce β-amino amides and acids from β-amino nitriles. The microorganisms show comparable trends: five-membered alicyclic 2-amino nitriles were transformed significantly faster than the six-membered compounds and the products of trans-2-amino nitriles (amides and acids) were formed considerably faster than the cis-counterparts (amides). The trans-five membered nitriles gave the amides (1b, 5b) in excellent enantiomeric excess (94-99%), the biotransformation of trans-six membered substrates resulted in the formation of the acid (3c, 7c) in excellent ee (87-99%). The ee's of the cis-compounds were throughout lower. Fifteen new substances were synthesized and characterized in the course of this work.     

Oligodeoxynucleotide analogues containing 3′-deoxy-3′-C-threo-hydroxymethylthymidine: Synthesis, hybridization properties and enzymatic stability

Novel Oligodeoxynucleotide analogues containing 3′-C-threo-methylene phosphodiester internucleoside linkages were synthesized on automated DNA-synthesizers using the phosphoramidite approach. The sugar modified phosphoramidite building block 5 was obtained by phosphitylation of 1-(2,3-dideoxy-5-O-(4,4′-dimethoxytrityl)-3-C-hydroxymethyl-β-D-threo-pentofuranosyl)thymine (4) which was synthesized in only three steps from 5′-O-(4,4′-dimethoxytrityl)thymidine (1). The hybridization properties and enzymatic stability of the oligonucleotide analogues were studied by UV experiments. 17-Mers having one or three modifications in the middle or two modifications in each end hybridized to DNA with moderate lowered affinity compared to unmodified 17-mers (ΔT_m 1–3°C per modification). Furthermore, the end-modified and all-modified oligonucleotides were stable towards snake venom phosphodiesterase.     

Influence of Test Specimen Geometry and Water Soaking on the In Vitro Cytotoxicity of Orthocryl®, Orthocryl® LC,Loctite® EA 9483 and Polypropylene

Depending on their composition, plastics have a cytotoxic potential that needs to be evaluated before they are used in dentistry, e.g., as orthodontic removable appliances. Relevant guidelines set out requirements that a potential new resin in the medical field must meet, with a wide scope for experimental design. In the present study, test specimens of different geometries consisting of varying polymers (Orthocryl^®, Orthocryl^® LC, Loctite^® EA 9483, Polypropylene) were soaked for different periods of time, then transferred to cell culture medium for 24 h, which was subsequently used for 24-h cultivation of A549 cells, followed by cytotoxicity assays (WST-1, Annexin V-FITC-propidium iodide (PI) flow cytometry). In this context, a reduction in the cytotoxic effect of the eluates of test specimens prepared from Orthocryl^® LC and Loctite^® EA 9483 was particularly evident in the Annexin V-FITC-PI assay when the soaking time was extended to 48 h and 168 h, respectively. Consistent with this, a reduced release of potentially toxic monomers into the cell culture medium, as measured by gas chromatography-mass spectrometry, was observed when the prior soaking time of test specimens of all geometries was extended. Remarkably, a significant increase in cytotoxic effect was observed in the WST-1 assay, which was accompanied by a higher release of monomers when the thickness of the test sample was increased from 0.5 to 1.0 mm, although an elution volume adapted to the surface area was used. However, further increasing the thickness to 3.0 mm did not lead to an increase in the observed cytotoxicity or monomer release. Test specimens made of polypropylene showed no toxicity under all test specimen sizes and soaking time conditions. Overall, it is recommended to perform toxicity studies of test specimens using different geometries and soaking times. Thereby, the influence of the different specimen thicknesses should also be considered. Finally, an extension of the test protocols proposed in ISO 10993-5:2009 should be considered, e.g., by flow cytometry or monomer analysis as well as fixed soaking times.     

Liquid-Liquid Equilibrium of Copolymer Solutions with Broad and Asymmetric Chemical Distributions

ABSTRACT

A solution of a random copolymer showing polydispersity only with respect to chemical composition is considered. A model distribution very flexible in its breadth and in its asymmetry is used to describe the polydispersity. Based on continuous thermodynamics, equations for the cloud-point curve, the shadow curve, the spinodal, the critical point, and the heterogeneous double critical point are derived. the activity coefficients are calculated with the aid of Huggins' χ-parameter concept assuming χ to depend linearly on the average chemical composition of the copolymer. the influence of the breadth and the asymmetry of the distribution on the liquid-liquid equilibrium of the copolymer solution is discussed.     

Do halogen and methyl substituents have electronic effects on the structures of simple disilanes? An experimental and theoretical study of the molecular structures of the series X3SiSiMe3 (X = H, F, Cl and Br)

The gas-phase molecular structures of a series of halogen-substituted disilanes [X₃SiSiMe₃ (X = H, F, Cl and Br)], 1,1,1-trimethyldisilane (H₃SiSiMe₃), 1,1,1-trifluoro-2,2,2-trimethyldisilane (F₃SiSiMe₃), 1,1,1-trichloro-2,2,2-trimethyldisilane (Cl₃SiSiMe₃) and 1,1,1-tribromo-2,2,2-trimethyldisilane (Br₃SiSiMe₃), have been determined in the gas phase by electron diffraction. Ab initio calculations at the HF and MP2 level were used to support the experimental investigation using the SARACEN method. All of the investigated structures were determined to adopt a staggered structure with C _3v symmetry. The effect of substitution on the Si–Si bond and the Si–Si–X bond angle was investigated and these results were compared to results obtained from a recent study of halogen-substituted disilanes [X₃SiSiXMe₂ (X = F, Cl, Br and I)] to consider the effect of the methyl groups on the substituted disilanes.