Secondary hypervalent I(III)...O interactions: synthesis and structure of hypervalent complexes of diphenyl-lambda3-iodanes with 18-crown-6

Reported here for the first time are the synthesis and characterization of supramolecular complexes between diaryl-lambda(3)-iodanes and 18-crown-6 (18C6). Slow evaporation of solvents afforded 1:1 and 2:1 complexes between Ph(2)IBF(4) and 18C6 as stable crystals, depending on the conditions. X-ray crystal structures of these complexes indicated that each iodine atom contacts with the three adjacent oxygen atoms of 18C6 through two hypervalent secondary bonding and a weak interaction. (1)H NMR analyses and CSI-MS spectra showed that, in dichloromethane solution, Ph(2)IBF(4) exclusively forms the 1:1 complex with 18C6 (binding constant K(a), 1.02 x 10(3) M(-)(1)). The binding constants decrease with the increased solvent donor ability (Gutmann's DN). Changing the heteroatom ligand from BF(4) to the less nucleophilic PF(6) and AsF(6) increased the binding constant by about six times. Substitution of an electron-withdrawing group onto the para position of Ph(2)IBF(4) tends to increase in the complex stability. A linear Hammett relationship (rho = 0.59) between log K(a) and sigma(p)(+) values of substituents indicates that the diaryl-lambda(3)-iodanes with electropositive iodine(III) interact more efficiently with 18C6. Decreased binding magnitude was measured with 15C5, dibenzo-18C6, dibenzo-21C7, and dibenzo-30C10.     

Screening effect diverts the swimming directions from diaphototactic to positive phototactic in a disk-shaped green flagellate Mesostigma viride

We found diaphototactic behavior (i.e. the cells swim perpendicularly with respect to the incident light) in a strain with colorless eyespot of a unicellular disk-shaped green flagellate Mesostigma viride. Lacking pigments completely in the eyespot, the screening effect in this strain was due only to the central part of the chloroplast whose cross section was thin. The diaphototaxis was most obvious when unilateral green stimulus light (520-580 nm) was given, whereas positive phototaxis appeared when given blue light (430-490 nm). The choice between diaphototaxis and (ordinary) phototaxis depended entirely on the transmission (%T) of the cell body against each wavelength of the stimulus: the green light penetrated well (%T > 90%), whereas the blue light was considerably shaded by the chloroplast (50% < %T < 70%). The fraction of positive phototactically behaving cells against each wavelength was in proportion to the front-to-back contrast value obtained at each individual wavelength. The fraction of diaphototaxis was inversely proportional to it. In addition, bilateral stimulus irradiations to wild-type cell with colored eyespot provided useful information about the principle of the diaphototactic steering.     

Evaluation of the evaporation behavior of Pd, Mo, Te, and Sb in simulated low level radioactive liquid waste

To sophisticate the nuclear fuel recycling processes, the transfer percentages for Pd, Mo, Te, and Sb should be determined. Each element solution containing NaNO₃ or HNO₃ was fed consistently into the thin film evaporator regulated in vac and at 50 °C. The analyte percentages in the inside of the lid, in the condenser, and in the distillate were 10^-1%/m², 10^-3%/m², and 10^-3% (DF = 10⁵), respectively. The Mo percentage in the condenser was lower by a factor of 10 than those of other elements investigated. The NO₃ ^- percentages were nearly constant despite increasing HNO₃ concentrations, however, the ratios decreased with increasing NaNO₃ concentrations.     

Electrolytic synthesis of ammonia in molten salts under atmospheric pressure

Ammonia was successfully synthesized by using a new electrochemical reaction with high current efficiency at atmospheric pressure and at lower temperatures than the Haber-Bosch process. In this method, nitride ion (N3-), which is produced by the reduction from nitrogen gas at the cathode, is anodically oxidized and reacts with hydrogen to produce ammonia at the anode.     

Preparation and characterization of polypropylene/mesoporous silica nanocomposites with confined polypropylene

Polypropylene (PP)/Ti-MCM-41 nanocomposites were prepared by isospecific propylene polymerization with Ti-MCM-41/Al(i-C₄H₉)₃ catalyst. The cross polarization/magic angle spinning (CP/MAS) ¹³C NMR spectrum of the composite was similar to that of the conventional isotactic PP, and the decrease in the pore volume of Ti-MCM-41 in the nanocomposites, as measured by N₂ adsorption, was consistent with the value calculated from the weight loss in the thermogravimetric analysis (TGA) curve; both these facts attest to propylene polymerization within the mesopores of Ti-MCM-41. Alkali treatment followed by extraction with o-dichlorobenzene allows us to extract the confined PP out of the Ti-MCM-41 mesopores. Although the PP/Ti-MCM-41 nanocomposites do not exhibit a crystalline melting point, the same PP when extracted from the mesopores showed a clear melting point at 154.7 °C; this indicates that the crystallization of PP confined in mesopores is strongly hindered. For the PP polymerized within the confinement, the molecular weight (M_w) and molecular weight distribution (M_w/M_n) were 84,000 and 4.3, respectively; these values were considerably smaller than those of the PP polymerized concurrently outside the Ti-MCM-41 mesopores (M_w = 200,000–450,000, M_w/M_n = 40–75). Therefore, the confinement also has a marked effect on the molecular weight of the PP. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 3324–3332, 2003     

Synthesis and Characterization of α,ω‐Heterofunctional Poly(ethylene oxide) Macromonomers

A novel α,ω‐heterofunctional poly(ethylene oxide) (PEO) macromonomer possessing methacryloyl and thienyl end groups was prepared by ring‐opening polymerization of ethylene oxide initiated by potassium thienylethoxide and termination of the living PEO ends with methacryloyl chloride. Incorporation of methacryloyl and thienyl groups was confirmed by free‐radical and oxidative polymerization processes, respectively, and by means of ¹H NMR analysis.

     

NMR analysis of lignins in CAD-deficient plants. Part 1. Incorporation of hydroxycinnamaldehydes and hydroxybenzaldehydes into lignins

Peroxidase/H2O2-mediated radical coupling of 4-hydroxycinnamaldehydes produces 8-O-4-, 8-5-, and 8-8-coupled dehydrodimers as has been documented earlier, as well as the 5-5-coupled dehydrodimer. The 8-5-dehydrodimer is however produced kinetically in its cyclic phenylcoumaran form at neutral pH. Synthetic polymers produced from mixtures of hydroxycinnamaldehydes and normal monolignols provide the next level of complexity. Spectral data from dimers, oligomers, and synthetic polymers have allowed a more substantive assignment of aldehyde components in lignins isolated from a CAD-deficient pine mutant and an antisense-CAD-downregulated transgenic tobacco. CAD-deficient pine lignin shows enhanced levels of the typical benzaldehyde and cinnamaldehyde end-groups, along with evidence for two types of 8-O-4-coupled coniferaldehyde units. The CAD-downregulated tobacco also has higher levels of hydroxycinnamaldehyde and hydroxybenzaldehyde (mainly syringaldehyde) incorporation, but the analogous two types of 8-O-4-coupled products are the dominant features. 8-8-Coupled units are also clearly evident. There is clear evidence for coupling of hydroxycinnamaldehydes to each other and then incorporation into the lignin, as well as for the incorporation of hydroxycinnamaldehyde monomers into the growing lignin polymer. Coniferaldehyde and sinapaldehyde (as well as vanillin and syringaldehyde) co-polymerize with the traditional monolignols into lignins and do so at enhanced levels when CAD-deficiency has an impact on the normal monolignol production. The implication is that, particularly in angiosperms, the aldehydes behave like the traditional monolignols and should probably be regarded as authentic lignin monomers in normal and CAD-deficient plants.     

Comprehensive characterisation of the E phase of 6-octyl-2-phenylazulene

Molecular dynamics in the soft crystal, E phase of 6-octyl-2-phenylazulene was studied by X-ray diffraction, and dielectric and Fourier transform infrared spectroscopies. Clear dielectric dispersion is observed due to the head-to-tail disordering in a kHz range around 400 K. The CH stretching frequencies exhibit more pronounced shifts at the phase transition point from the high-temperature ordered crystal to the E phase than that at the melting from the E phase to the isotropic liquid. The results are discussed in comparison with a typical E series, 4-n-alkyl-4′-isothiocyanatobiphenyl (n being the number of carbon atoms in the alkyl group).