Integral low-energy electron Mössbauer spectroscopic studies of the surfaces of carbon nanotube-nanocomposite powders

The surface state of CNTs-Fe-Al₂O₃ and CNTs-Fe-MgAl₂O₄ nanocomposite powders was studied by integral low-energy electron Mössbauer spectroscopy (ILEEMS). Several samples, prepared by reduction of α-(Al,Fe)₂O₃ or (Mg,Fe)Al₂O₄ precursors in a H₂-CH₄ atmosphere, were investigated, demonstrating that ILEEMS is a promising tool completing transmission Mössbauer spectroscopy for the investigation of the metal Fe and iron-carbide particles in the different carbon nanotube systems.     

Fluoride anion sensing using colorimetric reagents containing binaphthyl moiety and urea binding site

Four 1,1′-binaphthalene based bis-urea derivatives bearing aryl groups at end-on nitrogen atoms IIIa–d were synthesized as potential sensor molecules. These receptors show characteristic UV-VIS spectral changes on complexation with anions and they exhibit selective recognition of F⁻ over other halide anions. Interaction of a fluoride anion with urea NH groups was confirmed by ¹H NMR data. The presence of an electron-withdrawing nitro group in N′-aryls (receptors IIIa and IIIb) appeared to be necessary for naked-eye colorimetric detection. These receptors show dramatic color change from light-yellow to orange (IIIa) or to orange-red (IIIb) in the presence of guest fluoride anions already at concentrations of 10⁻⁵ mol dm⁻³ of the receptor and host.     

Use of near infrared emission spectroscopy in the study of supporting materials and stationary phases for liquid chromatography

Near infrared emission spectroscopy (NIRES) has been investigated in the study of different materials employed in liquid chromatography. The samples were heated in a nitrogen atmosphere and the emission spectra were obtained using a lab-made NIRES instrument. Through principal component analysis (PCA) using the raw emission spectra, it was possible to distinguish different materials according to their physical and/or chemical characteristics. Linear relationships between emissivity spectra and the contents of the coating material or the specific surface areas was observed for stationary phases or bare silicas, respectively. Furthermore, the thermal stability of stationary phases could be followed in real time.     

EELS performance measurements on a new high energy resolution imaging filter

In this paper we characterize the spectroscopy performance of a new high resolution electron energy-loss spectrometer for transmission electron microscopy, recently installed in our lab. With the event of commercially available monochromated transmission electron microscopes, equipped with improved spectrometers, experiments became feasible that allow the study of chemical bonding and electronic structures of atoms and solids at the nanometer level with an energy resolution in the range of 0.2-0.3 eV. This significant enhancement in resolution, however, can only be fully harnessed with an optimized microscope and spectrometer setup and in a suitable local environment. We attempt to quantify some of the limiting factors on our system with emphasis on spectrum mixing, spectrometer aberrations and transmissivity and we sketch proper working conditions in order to achieve the desired performance.     

Double-fold C-H oxygenation of arenes using PyrDipSi: a general and efficient traceless/modifiable silicon-tethered directing group

The efficient Pd-catalyzed double-fold C-H oxygenation of arenes into resorcinols using the newly developed 2-pyrimidyldiisopropylsilyl (PyrDipSi) directing group is described. Its use allows for the sequential introduction of OAc and OPiv groups in a one-pot manner to produce orthogonally protected resorcinol derivatives. The PyrDipSi group is superior to the previously developed 2-pyridyldiisopropylsilyl (PyDipSi) group, as it is efficient for monooxygenation of ortho-substituted arenes. Notably, the PyrDipSi group can be easily installed into arene molecules and can be easily removed or modified after the oxygenation reaction.     

A 32 vertex polyhedron via supramolecular assembly of silanedithiolate silanolate units

A high yield synthesis of the first silanedithiolate silanolate is reported which spontaneously assembles forming an inorganic rugby ball shaped 32 vertex polyhedral cluster stabilized by sterically demanding 2,6-dimesitylphenyl substituents and two LiCl units.     

Lectin from Canavalia brasiliensis seeds (ConBr) is a valuable biotechnological tool to stimulate the growth of Rhizobium tropici in vitro

To study the interactions between a Rhizobium tropici strain and lectins isolated from the seeds of Canavalia ensiformis (ConA) and Canavalia brasiliensis (ConBr), a lectin fluorescence assay was performed. In addition, an experiment was designed to evaluate the effect of the two lectins on bacterial growth. Both lectins were found to bind to R. tropici cells, but the interactions were inhibited by D-mannose. Interestingly, only ConBr stimulated bacterial growth in proportion to the concentrations used (15.6-500 μg/mL), and the bacterial growth stimulation was inhibited by D-mannose as well. Structure/Function analyses by bioinformatics were carried out to evaluate the volume and carbohydrate recognition domain (CRD) configuration of ConA and ConBr. The difference of spatial arrangement and volume of CRD may indicate the variation between biological activities of both lectins. The results suggest that ConBr could be a promising tool for studies focusing on the interactions between rhizobia and host plants.     

Design, synthesis, evaluation, and structure of vitamin D analogues with furan side chains

Based on the crystal structures of human vitamin D receptor (hVDR) bound to 1α,25-dihydroxy-vitamin D(3) (1,25 D) and superagonist ligands, we previously designed new superagonist ligands with a tetrahydrofuran ring at the side chain that optimize the aliphatic side-chain conformation through an entropy benefit. Following a similar strategy, four novel vitamin D analogues with aromatic furan side chains (3a, 3b, 4a, 4b) have now been developed. The triene system has been constructed by an efficient stereoselective intramolecular cyclization of an enol triflate (A-ring precursor) followed by a Suzuki-Miyaura coupling of the resulting intermediate with an alkenyl boronic ester (CD-side chain, upper fragment). The furan side chains have been constructed by gold chemistry. These analogues exhibit significant pro-differentiation effects and transactivation potency. The crystal structure of 3a in a complex with the ligand-binding domain of hVDR revealed that the side-chain furanic ring adopts two conformations.     

Unusual nonoctahedral geometry with molybdenum oxoimido complexes containing η2-pyrazolate ligands

The preparation and oxygen-atom-transfer (OAT) reactivity of oxoimido complexes [MoO(N-t-Bu)(t-Bu(2)-4-Rpz)(2)] [where R = H (1), Br (2), and Me (3); t-Bu(2)pz = 3,5-di-tert-butylpyrazolate] are reported. The reaction of the potassium salt of the respective pyrazolate ligands and the molybdenum oxoimido precursor, [MoO(N-t-Bu)Cl(2)(dme)] (dme = dimethoxyethane), in toluene afforded complexes 1-3 in good yields. The complexes were fully characterized by (1)H and (13)C NMR and IR spectroscopy, mass spectrometry, elemental analysis, and single-crystal X-ray crystallography. The solid-state structures reveal that, in each case, the molybdenum center is coordinated by one oxo, one N-t-Bu group, and two sterically demanding pyrazolate ligands via their two adjacent nitrogen atoms in an η(2) fashion. Coordination around the metal center is severely distorted from octahedral and might be seen as closely approaching a distorted trigonal-prismatic geometry, which is relevant to the active site of dimethyl sulfoxide reductase in its oxidized form. The potential utility of all of the complexes 1-3 for OAT reactivity toward PMe(3) at room temperature is examined, and plausible mechanistic pathways are explored by density functional theory calculations. Furthermore, the complexes reported here open a new and convenient entry into mixed oxoimidomolybdenum complexes.