Synthesis and structural characterization of some titanium butoxides modified with chloroacetic acids

Reactions of Ti(OBu^s)₄ and Ti(OBuⁿ)₄ with chloroacetic acids (mono-, di-, and tri-) were carried out in toluene in 1:1 and 1:2 molar ratios at room temperature to generate new precursors of titania. These modified alkoxides/oxo-alkoxides were characterized by spectroscopic methods. A solution of Ti(OBuⁿ)₂(OOCCCl₃)₂ in toluene left for crystallization at ?30 °C yielded single crystals of the product Ti₆(μ₂-O)₂(μ₃-O)₂(μ₂-OC₄H₉)₂(OC₄H₉)₆(OOCCCl₃)₈. Single-crystal X-ray diffraction revealed the molecular structure to be composed of a hexanuclear unit in which two Ti₂O₁₀ units (made by two edge-sharing octahedra) are linked with two corner-sharing octahedra.     

Spray-dried oil powder with ultrahigh oil content

We report a new facile route to the production of solid oil powders with an oil weight content of as high as 90% or beyond. The proposed method starts from a standard protein-stabilized oil-in-water emulsion in which a protein monolayer absorbed at the oil-water interface is successively cross linked by a thermal treatment. The emulsion is then spray dried as for ordinary emulsions, however without the addition of hydrocolloids typically needed when spray drying liquid oil dispersions. This leads to a final solid oil powder in which the total mass is constituted of oil, proteins, and eventual buffer salts and in which the elasticity of the cross-linked protein monolayer is alone sufficient to stabilize the powder and to limit any oil leakage. To best illustrate the potential in food applications and to preserve the food-grade nature of the constituents, we have used thermal denaturation at 80 °C for 15 min to cross link a β-lactoglobulin-stabilized olive oil-in-water emulsion and to produce the corresponding solid oil powder. Because of the simplicity and flexibility of the proposed pathway, the present method can be used inexpensively to convert any type of hydrophobic liquid into the corresponding solid powder and is then particularly suitable for cosmetic, pharmaceutical, medical, biotechnological, and food applications.     

Evaluation of the reliability of maize reference assays for GMO quantification

A reliable PCR reference assay for relative genetically modified organism (GMO) quantification must be specific for the target taxon and amplify uniformly along the commercialised varieties within the considered taxon. Different reference assays for maize (Zea mays L.) are used in official methods for GMO quantification. In this study, we evaluated the reliability of eight existing maize reference assays, four of which are used in combination with an event-specific polymerase chain reaction (PCR) assay validated and published by the Community Reference Laboratory (CRL). We analysed the nucleotide sequence variation in the target genomic regions in a broad range of transgenic and conventional varieties and lines: MON 810 varieties cultivated in Spain and conventional varieties from various geographical origins and breeding history. In addition, the reliability of the assays was evaluated based on their PCR amplification performance. A single base pair substitution, corresponding to a single nucleotide polymorphism (SNP) reported in an earlier study, was observed in the forward primer of one of the studied alcohol dehydrogenase 1 (Adh1) (70) assays in a large number of varieties. The SNP presence is consistent with a poor PCR performance observed for this assay along the tested varieties. The obtained data show that the Adh1 (70) assay used in the official CRL NK603 assay is unreliable. Based on our results from both the nucleotide stability study and the PCR performance test, we can conclude that the Adh1 (136) reference assay (T25 and Bt11 assays) as well as the tested high mobility group protein gene assay, which also form parts of CRL methods for quantification, are highly reliable. Despite the observed uniformity in the nucleotide sequence of the invertase gene assay, the PCR performance test reveals that this target sequence might occur in more than one copy. Finally, although currently not forming a part of official quantification methods, zein and SSIIb assays are found to be highly reliable in terms of nucleotide stability and PCR performance and are proposed as good alternative targets for a reference assay for maize.     

60]fullerene-pyrrolidine-N-oxides

Eight members of a new family of fullerene derivatives, [60]fulleropyrrolidine-N-oxides, have been synthesized and characterized. Facile oxidation, by a peracid, of the parent [60]fulleropyrrolidine gave clean conversions into the product molecules, in which the tertiary amine is transformed into a quaternary amine bearing an oxygen atom. The reaction is very selective, favoring the nitrogen atom of the pyrrolidine ring in preference to epoxidation of the fullerene cage. The 1H NMR shows an AB quartet splitting pattern, characteristic of nonequivalent hydrogens in the pyrrolidine ring and at a chemical shift displacement of 0.8 ppm downfield. Other methods of characterization are described, including MS, differential scanning calorimetry, thermogravimetric analysis, HPLC, UV/vis, and IR. Conclusive evidence for the formation of an N-oxide moiety is provided by the synthesis, oxidation, and NMR characterization of a novel [60]fulleropyrrolidine containing a 15N isotope, showing an 85 ppm downfield heteroatom chemical shift. Preliminary details of the effects of substitution on the reactivity of the pyrrolidine ring are also reported.     

Consolidating molecular AND logic with two chemical inputs

A novel molecular AND logic gate 1 is demonstrated based on the competition between fluorescence and photoinduced electron transfer (PET). It is constructed according to a 'receptor2-spacer-fluorophore-spacer-receptor1-spacer-fluorophore-spacer-receptor2' format where receptor1 is a tertiary amine, receptor2 is a benzo-15-crown-5 ether and the fluorophore is an anthracene moiety, which are separated from each other by methylene spacers. The fluorescence response in methanol is significantly enhanced only when both H+ and Na+ are the inputs at high enough concentrations in accordance with AND logic. Cs+ behaves similarly to Na+, but with a lower fluorescence enhancement, whereas the other alkali metal cations are not effective. Electrospray ionization mass spectrometry provides evidence for formation of 1:1 and 1:2 (1:metal) complexes with alkali cations, and formation of a 1:2:1 (1:metal:proton) complex in the additional presence of acid.     

Supercontinuum generation using continuous-wave multiwavelength pumping and dispersion management

We experimentally demonstrate that continuous-wave supercontinuum generation in optical fibers can be significantly enhanced by using both multiwavelength pumping and dispersion management. We show by detailed spectral analysis that continuum enhancement is achieved mainly through a combination of Raman-assisted modulation instabilities, soliton compression, and dispersive wave generation. With this technique, an 800 nm wide (from 1.2 to 2.0 microm) 2 W supercontinuum source is reported that uses a three-wavelength pump and a dispersion-tailored four-optical fibers arrangement.     

Quantum critical point of an itinerant antiferromagnet in a heavy fermion

A quantum critical point of the heavy fermion Ce(Ru(1-x)Rh(x))2Si2, (x = 0,0.03) has been studied by single-crystalline neutron scattering. By accurately measuring the dynamical susceptibility at the antiferromagnetic wave vector k3 = 0.35c*, we have shown that the inverse energy width gamma(k3), i.e., the inverse correlation time, depends on temperature as gamma(k3) = c1 + c2T((3/2)+/-0.1), where c1 and c2 are x dependent constants, in a low temperature range. This critical exponent 3/2 +/- 0.1 proves that the quantum critical point is controlled by that of the itinerant antiferromagnet.     

Phthalocyanine-pyrene conjugates: a powerful approach toward carbon nanotube solar cells

In the present work, a new family of pyrene (Py)-substituted phthalocyanines (Pcs), i.e., ZnPc-Py and H(2)Pc-Py, were designed, synthesized, and probed in light of their spectroscopic properties as well as their interactions with single-wall carbon nanotubes (SWNTs). The pyrene units provide the means for non-covalent functionalization of SWNTs via π-π interactions. Such a versatile approach ensures that the electronic properties of SWNTs are not impacted by the chemical modification of the carbon skeleton. The characterization of ZnPc-Py/SWNT and H(2)Pc-Py/SWNT has been performed in suspension and in thin films by means of different spectroscopic and photoelectrochemical techniques. Transient absorption experiments reveal photoinduced electron transfer between the photoactive components. ZnPc-Py/SWNT and H(2)Pc-Py/SWNT have been integrated into photoactive electrodes, revealing stable and reproducible photocurrents with monochromatic internal photoconversion efficiency values for H(2)Pc-Py/SWNT as large as 15 and 23% without and with an applied bias of +0.1 V.     

Effects of gamma irradiation on the DNA-protein complex between the estrogen response element and the estrogen receptor

Signaling by estrogens, risk factors in breast cancer, is mediated through their binding to the estrogen receptor protein (ER), followed by the formation of a complex between ER and a DNA sequence, called estrogen response element (ERE). Anti-estrogens act as competitive inhibitors by blocking the signal transduction. We have studied in vitro the radiosensitivity of the complex between ERα, a subtype of this receptor, and a DNA fragment bearing ERE, as well as the influence of an estrogen (estradiol) or an anti-estrogen (tamoxifen) on this radiosensitivity. We observe that the complex is destabilized upon irradiation with γ rays in aerated aqueous solution. The analysis of the decrease of binding abilities of the two partners shows that destabilization is mainly due to the damage to the protein. The destabilization is reduced when irradiating in presence of tamoxifen and is increased in presence of estradiol. These effects are due to opposite influences of the ligands on the loss of binding ability of ER. The mechanism that can account for our results is: binding of estradiol or tamoxifen induces distinct structural changes of the ER ligand-binding domain that can trigger (by allostery) distinct structural changes of the ER DNA-binding domains and thus, can differently affect ER-ERE interaction.