Reaction of dicobalt octacarbonyl with acetylene and carbon monoxide at low temperature and pressure: Formation of cyclic enone products

Dicobalt octacarbonyl is shown to react with acetylene and carbon monoxide under mild conditions in dimethoxyethane or benzene to produce, in low yields, bicyclo[3.3.0]octa-3,7-diene-2,6-dione, benzoquinone, and the cyclopentadienone-derived products 3a,4,7,7a-tetrahydro-2,7-methanoindene-1,10-dione, 1-indanone, tetracyclo[5.5.2.0^2,60^8,12]tetradeca-4,10,13-triene-3,9-dione, and tetracyclo[5.5.2.0^2,60^8,12]tetradeca-4,9,13-triene-3,11-dione. Possible mechanisms for the formation of these products are discussed.     

Hydrogen-Related Paramagnetic Centers in Ge-Doped Sol-Gel Silica Induced by γ-Ray Irradiation

We have studied the generation mechanisms of H(II) paramagnetic centers in Ge-doped silica by investigating up to 10⁴ mol ppm sol-gel Ge-doped silica materials. We have considered materials with the same concentrations of Ge but that are produced by two different densification routes that give rise to different concentrations of Ge-related oxygen deficient centers (GeODC(II)). These centers are characterized by an optical absorption band at ∼5.2 eV (B_2β band) and two related emissions at ∼3.2 eV and ∼4.3 eV. The GeODC(II) content was estimated by absorption and emission measurements. The H(II) centers were induced by room temperature γ-ray irradiation and their concentration was determined by electron paramagnetic resonance measurements. The comparison between the two kinds of materials, obtained by different preparations, shows that the GeODC(II) concentration increases with the Ge content and is enhanced by vacuum densification. The comparison of irradiated samples shows that beyond the already known process of conversion of preexisting GeODC(II) into H(II) centers, another generation process of H(II) centers is effective that involves irradiation induced GeODC(II).     

Solution NMR determination of the seating(s) of meso-nitro-etioheme-1 in myoglobin: implications for steric constraints to meso position access in heme degradation by coupled oxidation

The highly stereoselective cleavage of hemin in myoglobin by coupled oxidation has been attributed to steric barriers that leave more space near the alpha- than the other meso-positions. The steric barriers near meso positions in myoglobin have been investigated by establishing the thermodynamics and dynamics of possible seatings in the pocket of horse myoglobin of a four-fold symmetric etioheme I modified with a bulky nitro group at a single meso position. The cyanomet complex of this reconstituted myoglobin exhibits three sets of (1)H NMR resonances that are linked dynamically and occur in approximate populations ratios of 0.82:0.10:0.08. Two dimensional (1)H NMR has been used to assign the hemin and heme pocket resonances in the major isomer in solution and to determine that the hemin is oriented with the nitro group at the canonical gamma-meso position of native hemin. The dominance of this isomer is attributed to the solvent exposure of this portion of the hemin which stabilizes the highly polar nitro group. Using a combination of magnetization transfer among methyl groups of the three isomers due to "hopping" of the hemin about its normal, the assigned resonances of an isoelectronic, bis-cyano complex of meso-nitro-etioheme I, and the known essentially constant rhombic perturbation of heme pocket sites on the hyperfine shifts of heme methyl (Kolczak, U.; Hauksson, J. B.; Davis, N. L.; Pande, U.; de Ropp, J. S.; Langry, K. C.; Smith, K. M.; LaMar, G. N. J. Am. Chem. Soc. 1999, 121, 835-843); the two minor isomers are shown to place their bulky nitro group at the canonical delta-meso (8%) and alpha-meso positions (10%). The comparable population of the isomers with nitro groups at the hydrophobic alpha- and delta-meso positions dictates that, while the static crystal structure finds more room near the alpha-meso position, the deformation at minimal energetic expense near the alpha- and delta-meso positions is comparable. These results argue that factors other than simple steric influences control the selectivity of the ring cleavage in myoglobin.     

Influence of the distal his in imparting imidazolate character to the proximal his in heme peroxidase: (1)h NMR spectroscopic study of cyanide-inhibited his42-->ala horseradish peroxidase

The functional higher oxidation states of heme peroxidases have been proposed to be stabilized by the significant imidazolate character of the proximal His. This is induced by a "push-pull" combination effect produced by the proximal Asp that abstracts ("pulls") the axial His ring N(delta)H, along with the distal protonated His that contributes ("pushes") a strong hydrogen bond to the distal ligand. The molecular and electronic structure of the distal His mutant of cyanide-inhibited horseradish peroxidase, H42A-HRPCN, has been investigated by NMR. This complex is a valid model for the active site hydrogen-bonding network of HRP compound II. The (1)H and (15)N NMR spectral parameters characterize the relative roles of the distal His42 and proximal Asp247 in imparting imidazolate character to the axial His. 1D/2D spectra reveal a heme pocket molecular structure that is highly conserved in the mutant, except for residues in the immediate proximity of the mutation. This conserved structure, together with the observed dipolar shifts of numerous active site residue protons, allowed a quantitative determination of the orientation and anisotropies of the paramagnetic susceptibility tensor, both of which are only minimally perturbed relative to wild-type HRPCN. The quantitated dipolar shifts allowed the factoring of the hyperfine shifts to reveal that the significant changes in hyperfine shifts for the axial His and ligated (15)N-cyanide result primarily from changes in contact shifts that reflect an approximately one-third reduction in the axial His imidazolate character upon abolishing the distal hydrogen-bond to the ligated cyanide. Significant changes in side chain orientation were found for the distal Arg38, whose terminus reorients to partially fill the void left by the substituted His42 side chain. It is concluded that 1D/2D NMR can quantitate both molecular and electronic structural changes in cyanide-inhibited heme peroxidase and that, while both residues contribute, the proximal Asp247 is more important than the distal His42 in imparting imidazole character to the axial His 170.     

Photodynamic properties of amphiphilic derivatives of aluminum tetrasulfophthalocyanine

Photodynamic therapy (PDT) is a promising treatment modality that has recently been accepted in clinics as a curative or palliative therapy for cancer and other nonmalignant conditions. Phthalocyanines (Pc) are attractive photosensitizers for PDT because of their enhanced photophysical and photochemical properties. The overall charge and solubility of Pc play a major role in their potential usefulness for PDT. A series of amphiphilic derivatives of tetrasulfonated aluminum Pc (AlPcS4) was prepared by substituting one of the four sulfonate groups with aliphatic side chains of 4, 8, 12 and 16 carbon atoms. The photodynamic properties of the derivatives were compared with those of AlPcS4 and the adjacent disulfonated aluminum Pc. Parameters studied included reversed-phase high-performance liquid chromatography (HPLC) retention times, capacity to generate singlet oxygen (1O2), in vitro cell uptake and phototoxicity, as well as PDT response of transplantable EMT-6 tumors in mice. The monomerized AlPcS4 derivatives showed similar or higher capacities to generate 1O2 as compared with the parent AlPcS4 as measured from relative L-tryptophan photooxidation yields. A549 cell uptake of the AlPcS4 derivatives decreased in the following order: AlPcS4(C16) > AlPcS4(C12) > AlPcS4(C8) > AlPcS4(C4). Human low-density lipoprotein at high concentrations (40 micrograms/mL) completely prevented uptake, whereas at 4 micrograms/mL uptake was decreased for the more lipophilic compounds and yet remained unaffected for the more hydrophilic dyes. Using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay, A549 cell survival was assessed; it showed that photocytotoxic activity varied directly with the HPLC retention times, i.e. more hydrophilic compounds were less phototoxic. As 1O2 yields were similar for the four substituted AlPcS4 derivatives, it was postulated that the increased cytotoxic activity was caused by enhanced subcellular localization as a result of the long aliphatic side chains. These amphiphilic compounds proved to be photodynamically potent against the EMT-6 mouse mammary tumor model implanted in Balb/c mice. At dye doses of 0.2 mumol/kg and a fluence of 400 J/cm2 complete tumor regression was observed with no morbidity. The substitution of AlPcS4 with long aliphatic chains on the macrocycle greatly enhances its photodynamic efficacy both in vitro and in vivo.     

A resistometric investigation of the decomposition kinetics of Al-21·8 at.% Zn solid solution at 276 °C

Under the condition of nearly equilibrium concentration of vacancies, time dependence of the amount of isothermal transformation given byy=R/R _f was investigated whereR _f is the total structural change of resistivity on completion of the whole process andR is the measured resistivity change. The investigation was done on the 21·8 at.% (40·3wt.%) Zn alloy under the condition of relatively low supersaturation of a few degrees centigrade below the metastable _R solvus line. The total transformation involves four kinetic stages: the first two stages correspond probably to diffusion-controlled growth of the _R particles from the supersaturated solid solution and to the ripening of these particles till their conversion to the cubic phase takes place. The last two kinetic stages account analogously for the particles growth and ripening. Both _R and phases were identified by the transmission electron microscopy. When separating the individual stages, the approximation byy=1–exp [–(mt) ⁿ] of the amount of transformationy was used. The approximation allowed to get the starting values of both the time and the change of the structural part of the electrical resistance for individual stages and also to derive the parametersm _i, n_i which had to be redetermined for the individual separated stages. These data made it possible to synthetize the experimental curves ofR andy vs. time for the total transformation.It is a pleasure to thank Doc. Dr. V.Syneek CSc. for stimulating the author's interest in this problem and for providing helpful discussions. I also would like to express my thanks to Ing. P.Bartuka CSc. for the transmission electron microscopic study carried out to identify the particular phases. The author is indebted to Ing.V. íma for the preparation of the investigated alloy and to Mrs. A.Mendlová and Mr. P.Vyhlídka for technical assistance.     

Study of Segregation Effects and Fusion Between Lipid Vesicles by Combined Scanning Dilatometric and Calorimetric Measurements

Abstract

Scanning dilatometric and calorimetric measurements were performed in order to obtain information on correlations between various phenomena involving a lipid vesicle. Scanning dilatometry has been shown to be a fast and reliable tool which gives complementary information to that obtained using differential scanning calorimetry and also, provides a means with which to follow dynamic processes without the introduction of perturbing probes into the lipid matrix. The systems examined were vesicles built up from mixtures of neutral and charged lipids in the presence of mono- and divalent inorganic cations. The studied processes were the gel-liquid crystal transition, lateral phase separation in mixed lipid vesicles and fusion between vesicles.     

Multiaxial mechanical behavior of aramid fibers and identification of skin/core structure from single fiber transverse compression testing

The transverse and longitudinal mechanical properties of aramid fibers like Kevlar? 29 (K29) fibers are strongly linked to their highly oriented structure. Mechanical characterization at the single fiber scale is challenging especially when the diameter is as small as 15 µm. Longitudinal tensile tests on single K29 fibers and single fiber transverse compression test (SFTCT) have been developed. Our approach consists of coupling morphological observations and mechanical experiments with SFTCT analysis by comparing analytical solutions and finite element modeling. New insights on the analysis of the transverse direction response are highlighted. Systematic loading/unloading compression tests enable to experimentally determine a transverse elastic limit. Taking account of the strong anisotropy of the fiber, the transverse mechanical response sheds light on a skin/core architecture. More importantly, results suggest that the skin of the fiber, typically representing a shell of one micrometer in thickness, has a transverse apparent modulus of 0.2 GPa. That is around more than fifteen times lower than the transverse modulus of 3.0 GPa in the core. By comparison, the measured longitudinal modulus is about 84 GPa. The stress distribution in the fiber is explored and the critical areas for damage initiation are discussed. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 374–384     

Nonbinary convolutional codes derived from group character codes

New families of unit memory as well as multi-memory nonbinary convolutional codes are constructed algebraically in this paper. These convolutional codes are derived from the class of group character codes. The proposed codes have basic generator matrices, consequently, they are noncatastrophic. Additionally, the new code parameters are better than the ones available in the literature.