Synergistic extraction of rare earths(III) from chloride medium with mixtures of 1-phenyl-3-methyl-4-benzoyl-pyrazalone-5 and di-(2-ethylhexyl)-2-ethylhexylphosphonate

The synergistic effect of 1-phenyl-3-methyl-4-benzoyl-pyrazalone-5 (HPMBP, HA) and di-(2ethylhexyl)-2-ethylhexylphosphonate (DEHEHP, B) in the extraction of rare earths (RE) from chloride solutions has been investigated. Under the experimental conditions used, there was no detectable extraction when DEHEHP was used as a single extractant while the amount of RE(III) extracted by HPMBP alone was also low. But mixtures of the two extractants at a certain ratio had very high extractability for all the RE (III). For example, the synergistic enhancement coefficient was calculated to be 9.35 for Y3+, and taking Yb3+ and Y3+ as examples, RE3+ is extracted as RE(OH)A(2).B. The stoichiometry, extraction constants and thermodynamic functions such as Gibbs free energy change Delta G (-17.06kJmol(-1)), enthalpy change Delta H (-35.08kjmol(-1)) and entropy change Delta S (-60.47JK(-1)mol(-1)) for Y3+ at 298 K were determined. The separation factors (SF) for adjacent pairs of rare earths were calculated. Studies show that the binary extraction system not only enhances the extraction efficiency of RE(III) but also improves the selectivity, especially between La(III) and the other rare earth elements.

Extraction of rare earths(III) from nitrate medium with di-(2-ethylhexyl) 2-ethylhexyl phosphonate and synergistic extraction combined with 1-phenyl-3-methyl-4-benzoy l-pyrazolone-5

The extraction of trivalent rare earths ( RE) from nitrate solutions with di-(2-ethylhexyl) 2-ethylhexyl phosphonate (DEHEHP, B) and synergistic extraction combined with 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 (HPMBP, HA) were investigated. The extraction distribution ratios demonstrate a distinct "tetra effect," and Y lies between Tb and Dy when DEHEHP is used as a single extractant for RE. According to the corresponding separation factors (SF12) for adjacent pairs of rare earths, it could be concluded that DEHEHP could be employed for the separation of La from the other rare earths, and Y from light rare earths. The present work has also found that mixtures of HPMBP and DEHEHP have an evident synergistic effect for RE(III). Taking Y( III) as an example, a possible synergistic extraction mechanism is proposed. The enhancement of extraction in the binary system can be explained due to the species Y(NO3) (.) A(2) (.) HA (.) B formed. The synergistic enhancement coefficients ( R), extraction constants, formation constants and thermodynamic functions of the reaction were calculated.

Effects of acetic acid on product selectivity in gas phase oxidative dehydrogenation of cyclohexane

The effect of adding acetic acid on the product distribution in gas phase oxidative dehydrogenation of cyclohexane over alpha(1)-VOPO4 catalyst was investigated. The role of acetic acid in the reaction process was put forward. The proposed mechanism is that acetic acid take precedence of cyclohexane adsorbing on the active sites of alpha(1)-VOPO4 catalyst to form isolated active site. Thus, cyclohexene species can desorb quickly from the active sites, avoiding its deep oxidation dehydrogenation. Almost 100% selectivity to cyclohexene could be obtained when the molar ratio of acetic acid to cyclohexane was 12.9:1 at 450 degrees C, the conversion of cyclohexane was 6.9%.

Glucose-lowering activity of amino acid-N-phosphonic acid oxovanadium complexes and its interaction with DNA

Vanadium has well-documented lowering glucose properties both in vitro and in vivo. The design of new oxovanadium(IV) coordination compounds, intended for use as insulin-enhancing agents in the treatment of diabetes mellitus, can potentially benefit from a synergistic approach, in which the whole complex has more than an additive effect from its component parts. Biological testing with oxovanadium(IV) organic phosphonic acid, for insulin-enhancing potential included acute administration, by oral gavage in streptozotocin (STZ) diabetic rats. The complexes of oxovanadium(IV) amino acid-N-phosphonic acid exhibit higher lowering glucose activity in vivo. The interaction of the complexes of oxovanadium(IV) amino acid-N-phosphonic acid with DNA was investigated by agarose gel electrophoresis. The results indicated that these complexes have strong interaction with DNA.

Synthesis and structural characterization of a new molecule-based complex constructed from dodecamolybdophosphoric acid and imidazole

A new compound, (CH5N2)(3)(PMo12O40CH4N23H2O)-C-.-H-. (1), was synthesized and structurally characterized by elemental analyses, IR spectra, UV spectra, NMR spectra and ESR spectra. This is, to our knowledge, the first example of an imidazole-polyoxometalate species. The compound was recrystallized from N,N-dimethylformamide (DMF), and then black block-like crystals of (C3H5N2)(4)((PMoMo11O40)-Mo-V-O-VI)(.)4C(3)H(7)NO(.) 2H(2)O (2), were obtained. It crystallizes in a triclinic space group P (1) over bar with n=12.423(3) Angstrom, b=12.666(3) Angstrom, c=13.341(3) Angstrom, alpha=70.56(3)degrees, beta=71.16(3)degrees, gamma=64.18(3)degrees, V= 1742.3(6) Angstrom(3), Z=1, R1 = 0.0585, wR2 = 0.1885. An X-ray crystallographic study showed that the crystal structure is constructed by electrostatic attractions and hydrogen bonds between a dodecamolybdophosphoric anion and an imidazole. The imidazole and DMF molecules occupy cavities in a polyoxometalate lattice ordered along a c-axis. The structure of (2) is similar to that of (1) from a comparison of both IR spectra and TGA Curves.

Separation of scandium, yttrium and lanthanum in high-performance centrifugal partition chromatography with S-octyl phenyloxy acetic acid

Separation of scandium(III), yttrium(III) and lanthanum(III) was performed by high-performance centrifugal partition chromatography (HPCPC) employing the stationary phase of S-octyl phenyloxy acetic acid (CA-12). The liquid-liquid extraction behavior of CA-12 for Sc(III), Y(III) and La(III), the acidity of aqueous phase, and the operation conditions of HPCPC were examined. The retention volume (V-R) increased with the order of Y(III), La(III) and Sc(III) accompanied with the elution of the mobile phase in different pH, which is lowered from 4.6 to 2.1.

Determination of ascorbic acid by flow injection chemiluminescence suppression method

chemiluminescence suppression method for the determination of ascorbic acid based on Luminol-KIO4-H2O2-ascorbic acid system was established. The linear range for ascorbic acid is 1.0 x 10(-7) similar to 1.0 x 10(-5) mol/L and the detection limit is 6.0 x 10(-8) mol/L. The relative standard deviation (n = 11) is 1.0% for 8.0 x 10(-7) mol/L ascorbic acid. The method has been used to determine the content of ascorbic acid in tablets and injections with satisfactory results.

Resolution of 3,3 '-dioxo-1,1 '(3H,3 ' H)spirobi[isobenzofuran]-5,6,5 ' 6 '-tetracarboxylic acid and Optically active Polyimides thereof

3,3'-Dioxo-1.1'(3H.3'H)spirobi[isobenzofuran]-5,6,5',6 acid 1 was resolved successfully and the corresponding optically active polyimides PI were synthesized. The properties of the optically active PI and the racemic one were investigated. The results showed that the specific rotation of(-)-PI was about two times to that of the: (+)-PI, and the regularity of the optically active PI was higher than that of the racemic one.

Deoxyribonucleic acid sample preparation in scanning probe microscope

The process of deoxyribonucleio acid (DNA) sample preparation in scanning tunneling microscope (STM) and atomic force microscope (AFM) is reviewed. The main discussions are devoted to the methods, advantages or drawbacks and improvement of the DNA sample's immobilization and spreading.

Fabrication of layer-by-layer deposited multilayer films containing DNA and its interaction with methyl green

Multilayer films were fabricated by layer-by-layer electrostatic deposition techniques between poly(diallyIdimethylammonium chloride) (PDDA) and calf thymus DNA (CT DNA) on glassy carbon and quartz substrates. Electrochemical impedance spectroscopy (EIS), Fourier transform infrared (FTIR) spectroscopy and UV-vis spectroscopy demonstrated the uniform assembly of PDDA/DNA multilayer films, and X-ray photoelectron spectroscopy confirmed the elemental composition of the films. Moreover, the interaction of DNA in PDDA/DNA films with methyl green was investigated by UV-vis spectroscopy and circular dichroism (CD). (C) 2001 Elsevier Science B.V. All rights reserved.

Determination of some basic constants of sec-octylphenoxy acetic acid

In this work some basic constants of extractant Sec-Octylphenoxy acetic acid (CA-12) such as solubility (S) in water, dissociation constant (K-a) in aqueous solution, dimerization constant( K-2) and distribution constant (K-d) between water and haptane have been determined by two phase titration method. The results are as follows: S = 1.40 x 10(-4) mol/L, K-a = 3.02 x 10(-4), K-2 = 3.56 x 10(2), K-d = 4.06 x 10(2) (25 +/-0.5 degreesC).

Determination of p-toluene sulfonic acid in phenol matrix by capillary zone electrophoresis with ultraviolet detection

The p-toluene sulfonic acid (MA) in phenol matrix was separated and determined by capillary electrophoresis with ultraviolet detector. the effect of the concentration and pH of the buffer on separation was investigated. Cinnamic acid has been chosen as the internal standard from four compounds, the calibration curves of PTSA in 50 mg/L phenol matrix were obtained with and without the internal standard. The linear range was from 1.25 to 12.5 mg/L and the correlation coefficient was 0.9999 for both curves. The limit of detection of PISA was 0.75 mg/L at 3 times of SIN. Finally, the concentration of PTSA in four synthesized samples was determined with method of standard additions, and the effect of matrix was discussed. The values of MA in these samples were 1.01, 0.94, 1.56 and 0.00 mg/L respectively.

Synthesis and characterization of chiral smectic side-chain liquid crystalline polysiloxanes and ionomers containing sulfonic acid groups

The synthesis of new chiral smectic A (S-A) side-chain liquid crystalline polysiloxanes (LCPs) and ionomers (LCIs) containing 4-allyloxy-benzoyl-4-(S-2-ethylhexanoyl) p-benzenediol his ate (ABB) as mesogenic units and 4-[[4-(2-propenyloxy)phenyl] azo]benzensulfonic acid (AABS) as nonmesogenic units is presented. The chemical structures of the monomers and polymers are confirmed by FTIR spectroscopy or H-1-NMR. Differential scanning calorimetry (DSC), optical polarizing microscopy, and X-ray diffraction measurements reveal that all the polymers P-I-P-IV and ionomers P-V-P-VI exhibit S-A texture. The results seem to demonstrate that the tendency toward the S-A-phase region increases with increasing sulfonic acid concentration, and the thermal stability of the S-A phase is determined by the flexibility of the polymer backbones and the interactions of sulfonic acid groups. (C) 2001 John Wiley & Sons, Inc.

Sol-gel-derived graphite organosilicate composite electrodes bulk-modified with Keggin-type alpha-germanomolybdic acid

A novel inorganic-organic hybrid material incorporating graphite powder and Keggin-type alpha -germanomolybdic acid (GeMo12) in methyltrimethoxysilane-based gels has been produced by the sol-gel technique and used to fabricate a chemically bulk-modified electrode. GeMo12 acts as a catalyst, graphite powder ensures conductivity by percolation, the silicate provides a rigid porous backbone, and the methyl groups endow hydrophobicity and thus limit the wetting section of the modified electrode. The GeMo12-modified graphite organosilicate composite electrode was characterized by cyclic and square-wave voltammetry. The modified electrode shows a high electrocatalytic activity toward the reduction of bromate, nitrite and hydrogen peroxide in acidic aqueous solution. In addition, the chemically-modified electrode has some distinct advantages over the traditional polyoxometalate-modified electrodes, such as long-term stability and especially repeatability of surface-renewal by simple mechanical polishing.

Synthesis of poly(phenylenesulfidephenylenamine) by self-polycondensation of methyl-(4-anilinophenyl) sulfide with antimony pentachloride

Poly(phenylenesulfidephenylenamine)(PPSA) an alternating copolymer and the hybrid structure of poly(phenylene sulfide)(PPS) and polyaniline(PAn), was synthesized by self-polycondensation of methyl-(4-anilino-phenyl) sulfide with antimony pentachloride and by the acid-induced self-polycondensation of methyl-(4-anilino-phenyl) sulfoxide.