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.     

Halonickel(I) complexes

Summary The reduction of nickel(II) halides with NaBH₄ in the presence of different ligands, L=PPh₃, AsPh₃, SbPh₃, has been studied. With a molar ratio L/Ni=3, new complexes NiX(SbPh₃)₃, X=Cl, Br, I, were obtained. With a molar ratio L/Ni=2, dimeric species [NiXL₂]₂, X=Cl, Br, I; L=PPh₃, AsPh₃, SbPh₃, were isolated. They are unstable and decompose easily in the solid and rapidly in solution, so that pure samples were only identified for X=Cl, L=PPh₃, AsPh₃, SbPh₃; X=Br, L=PPh₃ and X=I, L=PPh₃. With a molar ratio L/Ni=1, complexes [NiXL]_n (probably polymeric) were obtained. They are very unstable and pure samples could only be isolated when X=Cl, L=PPh₃. Impure substances containing variable amounts of decomposition products were obtained in all the remaining cases. The chemical and structural behaviour of these complexes is discussed.     

Occurrence and analysis of estrogens and progestogens in river sediments by liquid chromatography-electrospray-mass spectrometry

In this study, an analytical procedure for the determination in sediment of the most abundant and/or physiological active estrogens (estradiol, estriol, estrone, ethynyl estradiol, and diethylstilbestrol) and progestogens (progesterone, norethindrone. and levonorgestrel) is described. The procedure includes ultrasonic extraction of the lyophilized sediment, clean-up with octadecylsilica cartridges, and analysis by liquid chromatography-diode array detection-mass spectrometry (LC-DAD-MS). MS detection is performed with an electrospray interface in the positive ion mode for determination of the progestogens and in the negative ion mode for determination of the estrogens. The method was applied to the determination of the target compounds in river sediments from the area of Catalonia. Estrogens and progestogens were found at concentrations usually in the low ng g(-1) range. Estriol and norethindrone were the compounds most frequently found whereas maximum concentrations in all sediment samples were obtained for ethynyl estradiol (22.8 ng g(-1)) and estrone (11.9 ng g(-1)). Detection limits were in the range of 0.04-1.00 ng g(-1). Preliminary conjectures with regards to the environmental behavior and impact of estrogens and progestogens in rivers are made. To the authors' knowledge, this is the first work reporting a detailed method for the analysis of estrogens and progestogens in river sediments and data on the environmental occurrence of both groups of compounds.     

Comparative testing of the flammability of upholstery textiles

Flash ignition temperatures of upholstery textiles were measured with a modified derivatograph, and the TG, DTG, DTA and T curves were also recorded. The results obtained with the newly-developed system were compared with those of the ASTM D 1929 test procedure and with the simultaneously recorded thermal analysis curves.

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Zusammenfassung Der Flammpunkt von Upholstery-Textilien wurde mittels eines modifizierten Derivatographen gemessen. TG-, DTG-, DTA- und T-Kurven wurden registriert. Die mit diesem neuentwickelten System erhaltenen Ergebnisse wurden mit den nach dem ASTM D 1929 Testverfahren erhaltenen und mit den simultan registrierten thermoanalytischen Kurven verglichen.

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, -, -, - -. , ASTM 1929 .

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Paper presented at the World Conference on Thermal Analysis, Madeira (Portugal), 1986.     

Testing the photocatalytic activity of cyanogen-and thiocyanogen-based inorganic polymers

The photocatalytic properties of some cyanogen-and thiocyanogen-based inorganic polymers, such as paracyanogens containing different metals (Hg, Ag, Cu), polythiocyanogens of different iodine contents, polycyanogen and poly (cyanogenthiocyanate), have been tested in two systems. Cu-containing paracyanogen and the iodine-poor polythiocyanogens catalyze the photoreduction of methylviologen under visible light, furthermore the Cu-containing paracyanogen catalyzes the photoreduction of water to hydrogen under UV irradiation.

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, , , , (Hg, Ag, Cu), , (), . , , , , , , -.

     

Stability and magnetic characterization of oleate-covered magnetite ferrofluids in different nonpolar carriers

This work describes the preparation and stability evaluation of suspensions consisting of hydrophobic magnetite nanoparticles dispersed in different organic solvents. The ferrite particles are covered by a shell of chemisorbed oleate ions following a procedure that is described in detail. The oleate-covered particles were dispersed in different organic solvents with dielectric constants, epsilon(r), ranging between 1.8 and 9, and the centrifugal field strength needed to remove particle aggregates formed during the synthesis was determined for the different liquid carriers used. A thermodynamic analysis demonstrated that the observed stability of the suspensions in liquids with epsilon(r) < 5 is well correlated with the very low lyophobic attraction between the particles. This can easily be surmounted by thermal agitation, since the van der Waals attraction is negligible. In contrast, for liquids with epsilon(r) > 9, the suspensions become unstable because of the combined action of the van der Waals and lyophobic attractions, the latter being dominant for very polar solvents. Finally, a complete magnetic characterization of the oleate-magnetite powder, as well as of several stable ferrofluids prepared with it, was carried out. From this characterization, the magnetic diameters and magnetic moments of the particles immersed in the different liquid carriers were estimated and compared to those corresponding to the dry magnetic particles. This made it possible to estimate the thickness of the nonmagnetic layer on the particles.     

Preparation and sedimentation behavior in magnetic fields of magnetite-covered clay particles

This work is devoted to the preparation of magnetite-covered clay particles in aqueous medium. For this purpose, magnetite nanoparticles were synthesized by a coprecipitation method. These magnetic particles are adhered to sodium montmorillonite (NaMt) particles in aqueous suspensions of both materials, by appropriate control of the electrolyte concentrations. The best condition to produce such heteroaggregation corresponds to acid pH and approximately 1 mol/L ionic strength, when the electrokinetic potentials (zeta-potential) of both NaMt and Fe3O4 particles have high enough and opposite sign, as demonstrated from electrophoresis measurements. When a layer of magnetite re-covers the clay particles, the application of an external magnetic field induces a magnetic moment in clay-magnetite particles parallel to the external magnetic flux density. The sedimentation behavior of such magnetic particles is studied in the absence or presence of an external magnetic field in a vertical direction. The whole sedimentation behavior is also strongly affected by the formation of big flocculi in the suspensions under the action of internal colloidal interactions. van der Waals and dipole-dipole magnetic attractions between magnetite-covered clay particles dominate the flocculation processes. The different relative orientation of the clay-magnetite particles (edge-to-edge, face-to-edge, and face-to-face) are discussed in order to predict the most favored flocculi configuration.     

Group 6 heteroatom- and non-heteroatom-stabilized carbene complexes. beta,beta'- and alpha,beta,beta'-annulation reactions of cyclic enamines

Cyclization reactions of group 6 Fischer carbene complexes with cyclopentanone and cyclohexanone enamines are described. Enamine 3a undergoes thermal alpha,beta,beta'-annulation with alkenylcarbene complexes 1 and 2 (THF, 60 degrees C), affording semibullvalenes 5. The metalate intermediates 6, resulting from beta,beta'-annulation of the enamines 3a and 4a, were quantitatively formed by running the reaction in hexane at room temperature. Acid-promoted demetalation of 6 afforded endo-2-bicyclo[3.2.1]octen-8-ones 7 and endo/exo-2-bicyclo[3.3.1]nonen-9-ones 8 (endo/exo = 5:1). Using (S)-methoxymethylpyrrolidine-derived enamines 3b and 4b,c allowed highly enantioenriched cycloadducts endo-(+)-7 as well as endo-(-)-8 and exo-(-)-8 to be accessed. The non-heteroatom-stabilized carbene complex 10 was formed from complex 6 by Me(3)SiOTf-promoted elimination of the methoxy group, characterized by (13)C NMR, and transformed into the organic compounds 7, 7-d, and 11 as well as into bicyclo[3.2.1]octan-2,8-diones 14 and cycloheptanones 15. On the basis of this sequence, enantioenriched cycloheptanones (+)-15 were efficiently prepared in one pot from carbene complexes 2 and enamine 3b (51-55% yield, 91-96% ee). Extension of this work to simple Fischer carbene complexes 16 allowed an appropriate way to generate the nonstabilized pentacarbonyl[(phenyl(alkyl)carbene]tungsten complex 17 to be designed, for which the thermal and chemical behavior leading to compounds 18-21 is described.     

Net analyte signal as a deconvolution-oriented resolution criterion in the optimisation of chromatographic techniques

The performance of two multivariate calibration measurements, multivariate selectivity (SEL(s)) and scalar net analyte signal (scalar NAS), as chromatographic objective functions (COFs), was investigated. Since both assessments are straightforwardly related to the quantification of analytes in the presence of interferents, they were expected to confer new features in the optimisation of compound resolution, not present in conventional assessments. These capabilities are especially interesting in situations of low resolution, where peak deconvolution becomes an attractive alternative. For comparison purposes, chromatographic resolution (R(s)) and peak purity (p(s)) were used as reference COFs. In order to correlate COFs with the probability of deconvolution error, an artificial peak crossing was used to generate 73 different peak arrangements, which were deconvolved using three different methods. SEL(s) exhibited the best correlation, which allowed predicting properly the risk of obtaining inaccurate deconvolutions. The optimisation of a poorly resolved mixture of 16 aromatic compounds by reversed-phase liquid chromatography with methanol-water and acetonitrile-water mobile phases was examined to investigate the differences in performance among the resolution criteria. In situations like these, SEL(s) tends to consider acceptable mobile phase compositions with partial coelution, which permits however the deconvolution with low errors. In contrast, p(s) selects compositions where the resolution of some compounds is sacrificed to enhance the separation of others. Scalar NAS was not so favourable as expected, since it depends on sampling frequency and peak widening. SEL(s) was not affected by these factors.     

Are electrocyclization reactions of (3Z)-1,3,5-hexatrienone and nitrogen derivatives pseudopericyclic? A DFT study

[reactions: see text] Electrocyclization reactions of (3Z)-1,3,5-hexatrienone and nitrogen derivatives were studied by performing density functional theory (DFT) calculations together with the 6-31+G* basis set. Reactants, products, and transition states for each reaction were localized and the IRC connecting reactants and products was also obtained. Magnetic properties were evaluated along the reaction path to elucidate the characteristics of the reactions studied. As obtained from the calculations, electrocyclization of (3Z)-1,3,5-hexatrienone is a pericyclic process, as indicated by a variety of indexes, such as Nucleus Independent Chemical Shift (NICS), anisotropy of the magnetic susceptibility, or anisotropy of the current-induced density (ACID). This reaction presents characteristics of pericyclic reactions despite the activation energy lowering relative to the electrocyclization of (4Z)-1,2,4,6-heptatetraene, and the relatively small NICS values observed in the transition state. Magnetic properties indicate that an enhancement of the aromaticity relative to reactants and products occurs revealing the absence of orbital disconnections on the cyclic loop of interacting orbitals. Only two reactions among those studied exhibit pseudopericyclic character due to the in-plane attack of the lone pair on nitrogen. In these cases, the reactions showed no barrier for the electrocyclization process, and no aromaticity enhancement was observed.