A potential model for the study of ices and amorphous water: TIP4P/Ice

The ability of several water models to predict the properties of ices is discussed. The emphasis is put on the results for the densities and the coexistence curves between the different ice forms. It is concluded that none of the most commonly used rigid models is satisfactory. A new model specifically designed to cope with solid-phase properties is proposed. The parameters have been obtained by fitting the equation of state and selected points of the melting lines and of the coexistence lines involving different ice forms. The phase diagram is then calculated for the new potential. The predicted melting temperature of hexagonal ice (Ih) at 1 bar is 272.2 K. This excellent value does not imply a deterioration of the rest of the properties. In fact, the predictions for both the densities and the coexistence curves are better than for TIP4P, which previously yielded the best estimations of the ice properties.     

Ligand adsorption on an activated carbon for the removal of chromate ions from aqueous solutions

The results presented in this work are related to the design of a guideline to develop specific properties at the surface of an activated carbon (AC). For this, two model aromatic compounds have been synthesized and their electrolytic behavior in aqueous solutions was studied by a potentiometric method. The textural characteristics of the activated carbon were determined by porosimetry methods. The nature of oxygen-carrying functions and the acid-base behavior of the AC surface were characterized by TPD and potentiometric titration methods, respectively. The adsorption and desorption equilibria of the aromatic compounds on activated carbon were measured in aqueous solutions, and the hysteresis between adsorption and desorption, which reveals irreversible adsorption, was discussed on the basis of the frontier orbital theory. HOMO and LUMO orbitals of the adsorbent and adsorbates were calculated, and irreversible adsorption was attributed to the small energy difference between HOMO and LUMO of the aromatic adsorbates and the adsorbent. Adsorption equilibria of K2CrO4 in aqueous solution on the AC alone and on the AC-aromatic ligand adsorbents, respectively, prove the efficient development of specific chemical functions at the carbon surface provided by the adsorbed aromatic compounds.     

Sugarcane bagasse pulps

Organosolv (ethanol/water and acetosolv) pulps were treated with Bacillus pumilus xylanase for 4, 8, and 12 h and compared with commercial Cartazyme HS xylanase-treated pulps. Treatment of ethanol/water pulps with B. pumilus xylanase increased viscosity by 40% in 8 h of treatment compared with pulps treated without enzyme. However, acetosolv pulps treated with B. pumilus xylanase lost viscosity. Ethanol/water pulps treated with Cartazyme had a viscosity of 18.5 cP in 4 h of treatment. In the acetosolv pulps treated with commercial enzyme, the loss of viscosity was 20% compared with pulps treated without enzyme. Ethanol/water pulps treated with B. pumilus and Cartazyme had similar effects: a 44% reduction in kappa number for pulps treated with enzyme followed by alkaline extraction compared with pulps treated with alkaline extraction. In acetosolv pulps treated with B. pumilus, the kappa number was from 12 to 18, compared with pulps treated without enzyme, which had a 40% reduction in 4 and 12 h and a 60% reduction in 8 h. Cartazyme-treated acetosolv pulps had a kappa number of 14 in 4 and 8 h of treatment. For 12 h of treatment, the kappa number was 8. Fourier transform infrared spectra of the pulps showed that enzyme-treated pulps had changes in the 1000 cm^?1 absorption owing to a C-O bond present in esters. Using principal component analysis, it is possible to differentiate the unbleached pulps and enzyme-treated pulps.     

The furan approach to oxacycles. Part 5: Synthesis of a chiral butenolide, building block towards biologically interesting natural products

We describe an efficient new approach for the synthesis of a chiral butenolide that is based on the oxidation of a chiral furan ring with singlet oxygen in the presence of Hünig’s base, followed by Luche reduction and in situ lactonization.     

In situ studies of methanol decomposition and oxidation on Pd(111) by PM-IRAS and XPS spectroscopy

Methanol decomposition and oxidation on Pd(111) at millibar pressure were studied by in situ polarization-modulation infrared reflection absorption spectroscopy (PM-IRAS), on-line gas chromatography and pre- and postreaction X-ray photoelectron spectroscopy (XPS). Various dehydrogenation products such as methoxy CH3O, formaldehyde CH2O, formyl CHO, and CO could be spectroscopically identified. Methanol oxidation proceeds via dehydrogenation to formaldehyde CH2O, which either desorbs or is further dehydrogenated to CO, which is subsequently oxidized to CO2. Carbonaceous overlayers that are present during the reaction may favorably affect the selectivity toward CH2O. The reaction takes place on metallic Pd, and no indications of an involvement of Pd surface oxide were observed.     

Fluorescence lifetime enhancement of organic chromophores attached to gold nanoparticles

We present for the first time experimental evidence of fluorescence lifetime enhancement of organic chromophores attached to metal nanospheres via radiative decay engineering. The hybrid system (HS) was a modified "diconjugated" molecular probe, 4-acetamido-4'-maleimidylstilbene-2,2'-dithiol (AMDT), covalently bound to the surface of 5-nm-diameter Au nanospheres by its two sulfur atoms, at a distance d < 1 nm and with its molecular axis parallel to the surface of the nanoparticle surface. We measured a fluorescence lifetime increase of a factor of 2 at room temperature (tau(AMDT) = (4.32 +/- 0.10) ns and tau(HS) = (8.73 +/- 0.23) ns) and a factor of 3.4 at 4.2 K (tau(AMDT) = (2.64 +/- 0.07) ns and tau(HS) = (7.96 +/- 0.14) ns). We also found that the fluorescence quantum yield of this hybrid system is not reduced, proof of a weak energy transfer between the molecular probe and the nanoparticle. These results demonstrate that a molecular dipole oriented parallel to the metal surface tends to be reduced by the coupling with its image.     

Setting up of recovery profiles: A tool to perform the compliance with recovery requirements for residue analysis

The use of the recovery term has presented some confusion in Analytical Chemistry. Recent IUPAC recommendations propose to distinguish between two terms: recovery or recovery factor, ℜ, and apparent recovery, ℜ*. Apparent recovery includes recovery factor and a new recovery term proposed in this paper, named calibration recovery, ℜ^C, which depends of the type of systematic error due to the matrix effect (constant and/or proportional) and is related to the applied calibration methodology. This paper highlights the dependence of the calibration recovery on the sample analyte concentration and, for extension, of the apparent recovery, defines the recovery profile, and makes evident the need to determine a “fit for purpose” analyte concentration interval to comply with a regulated recovery requirements. An approach to estimate the calibration recovery and its associated uncertainty in relation to the above-mentioned dependence is presented. The usefulness of the proposed methodology has been shown in the quantification of a pesticide by GC-ECD for assessing dermal exposure.     

Graphical analysis of electrochemical impedance spectroscopy of two consecutive irreversible electron transfers. 2. Zinc anodic dissolution in acid media

The graphical analysis of the impedance plots is used in the study of the electrodic systems that take place through two consecutive single electron transfers. The zinc anodic dissolution is studied by using this procedure. The characteristic points easily allow us to explain and to simulate the impedance behavior of this electrodic system according to the steady-state potential and the roughness of the working electrode. The direct procedure for parametrical identification from the graphical analysis allows us to reduce the time needed for an impedance experiment. This graphical analysis is suggested for studying thin coated galvanized steels.     

Biological Activity of Flavonoids Copper Complexes

Three flavonoid copper(II) complexes Cu₂(quercetin)(CH₃COO)₃(CH₃OH) ( 1 ), Cu(anthrarufin)(CH₃COO)·1/2H₂O ( 2 ) and Cu(naringin)(OCH₃)(CH₃OH)₂ ( 3 ) have been synthesized and characterized by elemental analysis, IR, electronic absorption and EPR (X‐band) spectroscopy. The complexes have a strong protective action over the Δsod1 mutant of S. cerevisiae against reactive oxygen radicals generated by an external source of free radicals (H₂O₂ or the superoxide‐generating, menadione). On the other hand, the complexes cleave DNA efficiently even in the absence of reducing agents. The main reactive oxygen species responsible for the DNA strand cleavage have been determined using radical scavengers. A probably mechanism of the DNA damage is proposed.