Optical electron transfer through 2,7-diethynylfluorene spacers in mixed-valent complexes containing electron-rich "(η2-dppe)(η5-C5Me5)Fe" endgroups

We report in this communication the study of the intramolecular electron transfer through a 2,7-diethynylfluorenyl spacer in the Fe(II)/Fe(III) mixed-valent (MV) complex [(η(2)-dppe)(η(5)-C(5)Me(5))FeC≡C(2,7-C(21)H(24))C≡CFe(η(5)-C(5)Me(5))(η(2)-dppe)][PF(6)] (1[PF(6)]). The complex is generated in situ by comproportionation from its homovalent dinuclear Fe(II) and Fe(III) parents (1 and 1[PF(6)](2)). It is shown that electronic delocalization is much more effective through a 2,7-fluorenyl than through a 4,4'-biphenyl bridging unit.     

An allelochemical from Myrica gale with strong phytotoxic activity against highly invasive Fallopia x bohemica taxa

We report the identification of the allelochemical 3-(1-oxo-3-phenylpropyl)-1,1,5-trimethylcyclo-hexane-2,4,6-trione, known as myrigalone A, from the fruits and leaves of Myrica gale. The structure of the compound was confirmed by high-resolution techniques (UV, MS and NMR analysis). The compound is phytotoxic towards classical plant species used for allelochemical assays and also against Fallopia x bohemica, a highly invasive plant. Application of either powdered dry leaves or dry fruits of M. gale also showed in vitro phytotoxic activity. We hypothesize that M. gale could be used as a green allelopathic shield to control Fallopia x bohemica invasion, in addition to its potential use as an environmentally friendly herbicide.     

Isolation and Structural Elucidation of Armeniaspirols A–C: Potent Antibiotics against Gram‐Positive Pathogens

In an antibiotic lead discovery program, the known strain Streptomyces armeniacus DSM19369 has been found to produce three new natural products when cultivated on a malt‐containing medium. The challenging structural elucidation of the isolated compounds was achieved by using three independent methods, that is, chemical degradation followed by NMR spectroscopy, a computer‐assisted structure prediction algorithm, and X‐ray crystallography. The compounds, named armeniaspirol A–C ( 2 – 4 ), exhibit a compact, hitherto unprecedented chlorinated spiro[4.4]non‐8‐ene scaffold. Labeling experiments with [1‐¹³C] acetate, [1,2‐¹³C2] acetate, and [U‐¹³C] proline suggest a biosynthesis through a rare two‐chain mechanism. Armeniaspirols displayed moderate to high in vitro activities against Gram‐positive pathogens such as methicillin‐resistant S. aureus (MRSA) or vancomycin resistant E. faecium (VRE). As analogue 2 was active in vivo in an MRSA sepsis model, and showed no development of resistance in a serial passaging experiment, it represents a new antibiotic lead structure.     

Polysaccharide-induced order-to-order transitions in lyotropic liquid crystals

We report on the order-to-order transitions of lyotropic liquid crystals formed by self-assembled monogylcerides and water in the presence of polysaccharides of various molecular weights. The phase diagram of monoglyceride-water-polysaccharide systems, their morphology, and the topology of liquid crystalline structures were determined by combining optical cross-polarization, oscillatory shear rheometry, and small-angle X-ray scattering. The presence of hydrophilic mono-, oligo-, and polysaccharides in the water domains of liquid crystalline phases resulted in a general decrease of the cubic-to-hexagonal transition temperature. Provided that the sugar could fit within the water channels, the decrease was observed to be dependent on the polysaccharide concentration but independent of its molecular weight. For isotropic bicontinuous cubic phases, monomeric sugars such as glucose were reported to shrink the lattice parameter of the structure without inducing phase transitions. However, when a polymeric form of glucose was used, such as dextran, transitions from the gyroidal Ia3d cubic phase to double diamond Pn3m cubic phases were observed at well-defined molecular weights of polysaccharide. These results were interpreted in terms of size exclusions of polymer sugars by the water domains of the liquid crystal phases as well as the different topologies of water channels. Molecular dynamics simulations of polysaccharides in the water environment were performed to support these findings.     

Comprehensive pore structure characterization of silica monoliths with controlled mesopore size and macropore size by nitrogen sorption, mercury porosimetry, transmission electron microscopy and inverse size exclusion chromatography

The porosity of monolithic silica columns is measured by using different analytical methods. Two sets of monoliths were prepared with a given mesopore diameter of 10 and 25 nm, respectively and with gradated macropore diameters between 1.8 and 7.5 microm. After preparing the two sets of monolithic silica columns with different macro- and mesopores the internal, external and total porosity of these columns are determined by inverse size-exclusion chromatography (ISEC) using polystyrene samples of narrow molecular size distribution and known average molecular weight. The ISEC data from the 4.6 mm analytical monolithic silica columns are used to determine the structural properties of monolithic silica capillaries (100 microm I.D.) prepared as a third set of samples. The ISEC results illustrate a multimodal mesopore structure (mesopores are pores with stagnant zones) of the monoliths. It is found by ISEC that the ratio of the different types of pores is dependent on the change in diameter of the macropores (serve as flow-through pores). The porosity data achieved from the mercury penetration measurement and nitrogen adsorption as well of scanning electron microscopy (SEM) and transmission electron microscopy (TEM) pictures are correlated with the results we calculated from the ISEC measurements. The ISEC results, namely the multimodal pore structure of the monoliths, reported in several publications, are not confirmed analyzing the pore structures of the different silica monoliths using all other analytical methods.     

High‐Pressure Synthesis of Manganese Oxyhydride with Partial Anion Order

The high‐pressure synthesis of a manganese oxyhydride LaSrMnO_3.3H_0.7 is reported. Neutron and X‐ray Rietveld analyses showed that this compound adopts the K₂NiF₄ structure with hydride ions positioned exclusively at the equatorial site. This result makes a striking contrast to topochemical reductions of LaSrMnO₄ that result in only oxygen‐deficient phases down to LaSrMnO_3.5. This suggests that high H₂ pressure plays a key role in stabilizing the oxyhydride phase, offering an opportunity to synthesize other transition‐metal oxyhydrides. Magnetic susceptibility revealed a spin‐glass transition at 24 K that is due to competing ferromagnetic (Mn²⁺–Mn³⁺) and antiferromagnetic (Mn²⁺–Mn², Mn³⁺–Mn³⁺) interactions.     

Copper bromide complexed by fluorinated macroligands: towards microspheres by ATRP of vinyl monomers in scCO2

We report the successful synthesis of poly(methyl methacrylate) (PMMA) by atom transfer radical polymerization using a catalyst ligated to a polymeric ligand having a dual role, i.e., the complexation of the copper salt and the stabilization of the growing PMMA particles; at the end of the polymerization, the catalyst is removed by supercritical fluid extraction leading to PMMA microspheres with low residual catalyst content.     

Europium‐Doped Mesoporous Titania Thin Films: Rare‐Earth Locations and Emission Fluctuations under Illumination

Herein, Eu^III‐doped 3D mesoscopically ordered arrays of mesoporous and nanocrystalline titania are prepared and studied. The rare‐earth‐doped titania thin films—synthesized via evaporation‐induced self‐assembly (EISA)—are characterized by using environmental ellipsoporosimetry, electronic microscopy (i.e. high‐resolution scanning electron microscopy, HR‐SEM, and transmission electron microscopy, HR‐TEM), X‐ray diffraction, and luminescence spectroscopy. Structural characterizations show that high europium‐ion loadings can be incorporated into the titanium‐dioxide walls without destroying the mesoporous arrangement. The luminescence properties of Eu^III are investigated by using steady‐state and time‐resolved spectroscopy via excitation of the Eu^III ions through the titania host. Using Eu^III luminescence as a probe, the europium‐ion sites can be addressed with at least two different environments within the mesoporous framework, namely, a nanocrystalline environment and a glasslike one. Emission fluctuations (⁵D₀→⁷F₂) are observed upon continuous UV excitation in the host matrix. These fluctuations are attributed to charge trapping and appear to be strongly dependent on the amount of europium and the level of crystallinity.