A high-spin iron(IV)-oxo complex supported by a trigonal nonheme pyrrolide platform

We report the generation and characterization of a new high-spin iron(IV)-oxo complex supported by a trigonal nonheme pyrrolide platform. Oxygen-atom transfer to [(tpa(Mes))Fe(II)](-) (tpa(Ar) = tris(5-arylpyrrol-2-ylmethyl)amine) in acetonitrile solution affords the Fe(III)-alkoxide product [(tpa(Mes2MesO))Fe(III)](-) resulting from intramolecular C-H oxidation with no observable ferryl intermediates. In contrast, treatment of the phenyl derivative [(tpa(Ph))Fe(II)](-) with trimethylamine N-oxide in acetonitrile solution produces the iron(IV)-oxo complex [(tpa(Ph))Fe(IV)(O)](-) that has been characterized by a suite of techniques, including mass spectrometry as well as UV-vis, FTIR, M?ssbauer, XAS, and parallel-mode EPR spectroscopies. Mass spectral, FTIR, and optical absorption studies provide signatures for the iron-oxo chromophore, and M?ssbauer and XAS measurements establish the presence of an Fe(IV) center. Moreover, the Fe(IV)-oxo species gives parallel-mode EPR features indicative of a high-spin, S = 2 system. Preliminary reactivity studies show that the high-spin ferryl tpa(Ph) complex is capable of mediating intermolecular C-H oxidation as well as oxygen-atom transfer chemistry.     

Polytheonamides A and B, highly cytotoxic, linear polypeptides with unprecedented structural features, from the marine sponge, Theonella swinhoei

Polytheonamides A and B are highly cytotoxic polypeptides with 48 amino acid residues isolated from the marine sponge, Theonella swinhoei. The structure of polytheonamide B was determined by spectral and chemical methods, especially extensive 2D NMR experiments, which resulted in the unprecedented polypeptide structure; the N-terminal glycine blocked with a 5,5-dimethyl-2-oxo-hexanoyl group, the presence of eight tert-leucine, three beta-hydroxyvaline, six gamma-N-methylasparagine, two gamma-N-methyl-beta-hydroxyasparagine, and beta,beta-dimethymethionine sulfoxide residues. More significantly, it has the sequence of alternating D- and L-amino acids. Polytheonamide A is an epimer of polytheonamide B differing only in the stereochemistry of the sulfoxide of the 44(th) residue.     

High Refractive-Index Microspheres as Optical Cavity Structure

Microspheres of refractive index of n_D > 2.0 have been investigated. The organic-inorganic hybrid microspheres of n_D = 1.72 were prepared by the vibrating orifice technique using titanium-tetra-n-butoxide (TTBu) and diphenyldimethoxysilane (DPhDMS). For lasing demonstration, Eu³⁺-doped microspheres were prepared using europium (III) thenoyltrifluoroacetonate [Eu(TTFA)₃] as the dopant. The particles have good spherical shape, smooth surface and high optical transparency. The diameters of the particles could be controlled to within 0.1 m. Subsequent heating of the microspheres at 550°C under oxygen atmosphere resulted in an increase in the refractive index up to n_D = 2.6 with retention of the spherical shape. Resonant emission was confirmed from Eu^{3 +}-doped microspheres after heating at 400–550°C, by pumping with the 514.5 nm line of a CW- Ar⁺laser.     

Novel carbohydrate-appended metal complexes for potential use in molecular imaging

Seven discrete sugar-pendant diamines were complexed to the {M(CO)(3)}(+) ((99m)Tc/Re) core: 1,3-diamino-2-propyl beta-D-glucopyranoside (L(1)), 1,3-diamino-2-propyl beta-D-xylopyranoside (L(2)), 1,3-diamino-2-propyl alpha-D-mannopyranoside (L(3)), 1,3-diamino-2-propyl alpha-D-galactopyranoside (L(4)), 1,3-diamino-2-propyl beta-D-galactopyranoside (L(5)), 1,3-diamino-2-propyl beta-(alpha-D-glucopyranosyl-(1,4)-D-glucopyranoside) (L(6)), and bis(aminomethyl)bis[(beta-D-glucopyranosyloxy)methyl]methane (L(7)). The Re complexes [Re(L(1)-L(7))(Br)(CO)(3)] were characterized by (1)H and (13)C 1D/2D NMR spectroscopy which confirmed the pendant nature of the carbohydrate moieties in solution. Additional characterization was provided by IR spectroscopy, elemental analysis, and mass spectrometry. Two analogues, [Re(L(2))(CO)(3)Br] and [Re(L(3))(CO)(3)Br], were characterized in the solid state by X-ray crystallography and represent the first reported structures of Re organometallic carbohydrate compounds. Conductivity measurements in H(2)O established that the complexes exist as [Re(L(1)-L(7))(H(2)O)(CO)(3)]Br in aqueous conditions. Radiolabelling of L(1)-L(7) with [(99m)Tc(H(2)O)(3)(CO)(3)](+) afforded in high yield compounds of identical character to the Re analogues. The radiolabelled compounds were determined to exhibit high in vitro stability towards ligand exchange in the presence of an excess of either cysteine or histidine over a 24 h period.     

Application of Hot Press Sintering to Na2O-B2O3-SiO2 Gels Containing Quantum Dots for Lowering of Densification Temperature

Na₂O-B₂O₃-SiO₂ (NBS) gels containing a large amount of CdS quantum-dots (10 wt%) were densified using the hot press (HP) sintering method. By HP treatment, full-densification temperature could be lowered by about 40°C than that of the normal non-pressing (NP) heat treatment. Exciton absorption of CdS quantum-dots in HP-sample showed a large blue shift compared with that in the NP sample, and the size-distribution of CdS dots remained very sharp, with a mean particle diameter d = 3.66 nm and a standard deviation of = 0.72. HP pressure had a large effect on the reduction of sintering temperature and time, resulting in the suppression of the aggregation and growth of CdS quantum-dots in NBS glasses.     

Oxygen‐sensing properties of 5,10,15,20‐tetraphenylporphinato platinum(II) and palladium(II) covalently bound on poly(isobutyl‐co‐2,2,2‐trifluoroethyl methacrylate)

A novel methacrylate monomer bearing 5,10,15,20‐tetraphenylporphyrinato palladium(II) (PdTPP) (monomer 1a ) was synthesized and copolymerized with isobutyl methacrylate (IBM) and 2,2,2‐trifluoroethyl methacrylate (TFEM) to give poly (IBM‐co‐TFEM) bearing PdTPP (copolymer 2a ) as a dye‐conjugated oxygen‐permeable polymer for pressure‐sensitive paint applications. The introduction of PdTPP into copolymer 2a was confirmed by UV–vis spectroscopy and extended X‐ray absorption fine structure analysis. The Stern–Volmer plots of the copolymer 2a and a mixture of PdTPP and poly(IBM‐co‐TFEM) both showed downward curvature, unlike that of the platinum complex analogue (copolymer 2b ) previously reported. The plots were successfully fitted with a two‐site model to give two distinct Stern–Volmer constants (K_SV1 and K_SV2) and the partition ratio f₁. Interestingly, the f₁ values for the copolymer 2a were almost constant at about 0.98, whereas those of the mixture of PdTPP and poly(IBM‐co‐TFEM) increased from 0.889 to 0.967 as the temperature was increased. This finding suggests that there are two distinct microheterogeneities, one temperature‐dependent and the other temperature‐independent, in the mixture of PdTPP and poly(IBM‐co‐TFEM). The dye‐conjugation approach effectively eliminates the temperature‐dependent, but not the temperature‐independent microheterogeneity. The luminescence decays of copolymers 2a and 2b and the corresponding mixtures in the absence of oxygen indicated that the temperature‐dependent microheterogeneity involves an oxygen diffusion process, whereas the temperature‐independent one appears to be inherent nature in PdTPP. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 663–670, 2010     

Reductive carboxylation of alkyl halides with CO2 by use of photoinduced SmI2/Sm reduction system

Upon visible-light irradiation, reductive carboxylation of alkyl halides takes place by using a SmI₂/Sm mixed system under atmospheric CO₂ to afford the corresponding carboxylic acids in good to excellent yields.     

Comparison of the characteristics of cellulose microfibril aggregates isolated from fiber and parenchyma cells of Moso bamboo (<Emphasis Type="Italic">Phyllostachys pubescens)</Emphasis>

This study examined the relationship between the functions of plant cells and the characteristics of cellulose microfibril aggregates in the cell walls. For this purpose, the mature bamboo (Phyllostachys pubescens) culm was separated into fiber and parenchyma cells, and then the morphological and physical properties of the cellulose microfibril aggregates isolated from both cells were compared. SEM observations revealed that both fiber and parenchyma cells consist of similar microfibril aggregates approximately 15–20 nm in width. Moreover, X-ray analysis and the tensile tests of the sheets prepared from the microfibril aggregates showed that the cellulose microfibrils isolated from fiber and parenchyma cells had almost the same cellulose crystallinity and longitudinal Young’s modulus in the dry state. These results suggest that all the cellulose microfibrils synthesized in the same individual exhibit the same characteristics in the dry state regardless of cell function.     

Bending properties and cell wall structure of alkali-treated wood

Bending tests and X-ray diffraction studies were conducted on oven-dried wood samples (Picea jezoensis Carr.) treated with various concentrations of aqueous NaOH solution to investigate the influence of alkali treatment on the longitudinal contraction, bending properties, and cellulose structure. The length of the wood samples decreased and the density increased at NaOH concentrations greater than 10%. The Young’s modulus and the specific Young’s modulus decreased and the strain at yield increased for the same concentration range. However, the stress at yield was almost constant for all concentration ranges. X-ray diffraction analysis showed that lattice transformation from cellulose I to cellulose II did not occur during alkali treatment and the crystallinity index decreased at NaOH concentrations greater than 10%. The crystallinity index was linearly correlated with the changes in longitudinal contraction and the bending properties, which indicates that the increase in the proportion of amorphous components of the cellulose influences the longitudinal contraction and the bending properties of wood samples during alkali treatment.