The role of variable surface charge and surface complexation in the adsorption of humic acid on magnetite

The ionic strength dependence of humic acid (HA) adsorption on magnetite (Fe₃O₄) was investigated at pH 5, 8 and 9, where variable charged magnetite is positive, neutral and negative, respectively. The adsorption studies revealed that HA has high affinity to magnetite surface especially at lower pH, where interacting partners have opposite charges. However, in spite of electrostatic repulsion at pH 9 notable amounts of humate are adsorbed. Increasing ionic strength enhances HA adsorption at each pH due to charge screening. The dominant interaction is probably a ligand-exchange reaction, nevertheless the Coulombic contribution to the organic matter accumulation on oxide surface is also significant under acidic condition. The results from size exclusion chromatography demonstrate that the smaller size HA fractions enriched with functional groups are adsorbed preferentially on the surface of magnetite at pH 8 in dilute NaCl solution.     

Determination of Dextromethorphan and its Metabolite Dextrorphan in Human Hair by Gas Chromatography–Mass Spectrometry

An analytical method has been developed for determination of dextromethorphan (DMP) and dextrorphan (DRP) in human hair by gas chromatography–mass spectrometry (GC–MS). Hair samples (30 mg) were washed with distilled water and acetone and cut into small fragments (<1 mm) before extraction with methanol. The extracts were evaporated to dryness and then derivatized by use of BSTFA containing 1% TMCS, for preparation of the trimethylsilyl (TMS) derivative of DRP. The extract (1 μL) was then injected into the GC–MS. Recoveries of DMP and DRP at 7.0 and 22.5 ng mg^?1 were in the range 90.6–97.2% with intra-assay and inter-assay precision of less than 5.7% and 4.7%, respectively. LOD and LOQ were, respectively, 0.67 and 2.13 ng mg^?1 for DMP and 0.14 and 0.47 ng mg^?1 for DRP. The responses were linear with correlation coefficients (r > 0.9995) for the drugs studied. The applicability of the method was proven by analysis of authentic hair samples.     

Kinetics of the degradation of polystyrene in supercritical acetone

The kinetic analysis of the degradation of polystyrene (PS) in supercritical acetone has been studied using the nonisothermal weight loss technique with heating rates of 3, 5 and 7 °C/min. The weight loss data according to degradation temperature have been analyzed using the integral method based on Arrhenius form to obtain the kinetic parameters such as apparent activation energy and overall reaction order. The kinetic parameters obtained from this work were also compared with those of the thermal degradation of PS in nitrogen atmosphere. From this work, it was found that the activation energies of PS degradation in supercritical acetone were 73.3-200.7 kJ/mol and lower than those of the thermal degradation in nitrogen atmosphere.     

The Mitsunobu Inversion Reaction of Sterically Hindered 17-Hydroxy Steroids

The Mitsunobu inversion reaction of 3-methoxyestra-1,3,5(10)-trien-17-ol is dramatically influenced by the acidic component. There appears to be a relationship between the dissociation constant of the electron-withdrawing substituent on the aryl acid and the overall effectiveness of the reaction, with more acidic species generally providing a higher yield of inverted product.     

Selective hydrogenations of steroids catalyzed by heterogenized Ru complexes

Summary [RuCl₂(PPh₃)₃], [{RuCl₂(TPPMS)₂}₂] and their heterogenized analogs were applied in the selective hydrogenation of 17-keto- and α,β-unsaturated ketosteroids. In basic conditions these complexes selectively hydrogenated the C=O bonds, similarly to the results obtained in the case of α,β-unsaturated aldehydes. A new method was developed for the synthesis of an expensive steroid alcohol, which can be prepared traditionally in a more complicated way.     

Electron diffraction studies of the molecular structures of iron(II) chloride and iron(II) bromide. Evidence on the structure of dimeric species Fe2Br4

An expression for the extreme values of mean-square amplitudes of vibrations in polyatomic molecules has been derived which permits estimation of the mean-square amplitude without solving the vibrational problem. This expression can be improved for the stretching and scissoring modes when the assignment of frequencies is known. In turn, the corresponding vibrational frequency may be estimated from the experimental value of the mean-square amplitude. The mean-square amplitudes of the butadiene-1,3 molecule are considered as an example.     

Cyclocondensation reaction of a 1,5-diketone with 1,2-diamines

Reaction of 2-acetonyl-4,5-dimethoxy-3′-chlorobenzophenone (1) with ethylenediamine afforded the imidazo[2,1-a]isoquinoline 2, whereas 6-(3-chlorophenyl)-8,9-dimethoxybenzo[b]phenazine (3) and naphthol 4 were obtained with ortho-phenylenediamine.     

Complexity of intercalation of hydrazine into kaolinite--a controlled rate thermal analysis and DRIFT spectroscopic study

Controlled rate thermal analysis (CRTA) allows the separation of adsorbed and intercalated hydrazine. CRTA displays the presence of three different types of hydrogen-bonded hydrazine in the intercalation complex: (a) The first is adsorbed loosely bonded on the kaolinite structure fully expanded by hydrazine-hydrate and liberated between approx 50 and 70 degrees C (b) The second intercalated hydrazine is lost between approx 70 and 85 degrees C. (c) The third type of intercalated-hydrazine molecule is lost in the 85-130 degrees C range. CRTA at 70 degrees C enables the removal of hydrazine-water and results in the partial collapse of the hydrazine-intercalated kaolinite structure to form a hydrazine-intercalated kaolinite. Removal of the adsorbed hydrazine enables the DRIFT spectra of the hydrazine-intercalated complex without any adsorbed hydrazine to be obtained. A band at 3626 cm(-1) attributed to the inner surface hydroxyls of kaolinite hydrogen bonded to hydrazine is observed. The intercalation of hydrazine-hydrate into kaolinite is complex and results from the different types of surface interactions of the hydrazine with the kaolinite surfaces.     

Effect of nature of support and impregnating agent on lipophilicity determination for nonionic surfactants by reversed-phase thin-layer chromatography

Summary The retention of 9 nonylphenyl ethylene oxide oligomers was determined in 15 reversed-phase chromatographic systems using silicone oils of various molecular mass as impregnating agents and silica, cellulose and alumina supports. The data were evaluated with principal component analysis carried out on the covariance and the correlation matrices. The R_M values did not follow the additivity rule and they did not change linearly with increasing length of the ethylene oxide chain. This is probably due to the folded state of the chain in the eluent. The molecular mass of the silicone oils had a negligible effect on the retention whereas the retention increased with increasing level of impregnation. The support considerably influenced the lipophilicity values of these nonionic surfactants and cellulose seemed to be the most appropriate support. Calculations proved that the application of a correlation matrix may cause data distortion; therefore, the use of a covariance matrix is strongly proposed.     

Thermoanalytical Study of O,O'-Dibenzoyl-(2R,3R)-Tartaric Acid Supramolecular Compounds Part II. Investigation of the resolution of racemic alcohols

The resolution of three chiral alcohols with O,O'-dibenzoyl-(2R,3R)-tartaric acid (DBTA) via diastereoisomeric supramolecular compound formation was investigated with thermoanalytical methods. On the basis of TG measurements the DBTA:chiral alcohol molar ratio in the compounds is 1:1 which agrees with the results of single-crystal X-ray diffraction analysis. The DBTA – chiral alcohol supramolecular compounds have different supramolecular structure than the DBTA – achiral alcohol supramolecular compounds. The supramolecular compounds containing cyclohexanols have higher thermal stability than the compounds containing acyclic aliphatic alcohols. The amount of unreacted DBTA monohydrate in the solid phase can be determined both with DSC and with TG measurements. This revised version was published online in August 2006 with corrections to the Cover Date.