Effect of extractant on arsenic(V) recovery from sulfuric acid solutions

Extraction of arsenic(V) from sulfuric acid solutions with various extractants in multistage counter-current extraction-stripping systems was compared. The extraction ability of the extractants studied showed the following order: ENIM 100>TBP=CYANEX 923>2-methylhexanol. The extraction depends significantly on the number of extraction stages and the phase ratios in extraction. The effects of the number of stripping stages and the phase ratio in stripping are less important.     

Flotation—spectrophotometric determination of osmium with thiocyanate and methylene blue

A sensitive flotation—spectrophotometric method, based on the ion associate formed by the anionic thiocyanate complex of osmium with the basic dye methylene blue (MB) is described. The ion associate precipitates when the aqueous solution is shaken with toluene, and the separated and washed compound is dissolved in acetone. The molar absorptivity is 2.2 × 10⁵ l mol^-1 cm^-1 at 655 nm. Beer's law is obeyed. The molar ratio of Os:SCN:MB in the separated and washed ion associate is 1:6:3. Ruthenium reacts similarly. The method is applied to the determination of traces of osmium in crucible platinum after separation of osmium by distillation as tetroxide.     

Interaction of water with the regenerated cellulose membrane studied by DSC

One to three endothermal peaks atributted to melting of bulk and interfacial water were observed by DSC in the regenerated cellulose — water system. The profiles of thermal effects depend on water content, time of conditioning, film pretreatment and the conditions applied during the preceding freezing-thawing cycles. The occurrence might be deduced of melting-crystallisation processes. A large amount of non-freezable strongly bounded water was also detected. Although cellulose absorbs water quickly after immersion, the structural changes consisting on ordering of polymer fraction occur during further conditioning due to increase in strength of water binding. Using the membranes in the separation module at 90°C causes weakening of these bonds. Differences between interaction of particular cellulose films with water can be detected during the first, the second and the third heating. This revised version was published online in July 2006 with corrections to the Cover Date.     

Improvement in the synthesis of metallophthalocyanines using microwave irradiation

A successful application of microwave irradiation, in which phthalocyanines were synthesized under solventless conditions from 1,2-phthalonitrile or phthalic anhydride and urea in the presence of metal templates is described. It was found that in comparison with conventional heating, the microwave process is a very useful alternative for cyclotetramerization processes because of reduction of the reaction time, better yield, and easy-to-perform procedure.     

Novel design of a pentacyclic scaffold as structural mimic of saframycin A

The design, synthesis and evaluation of a pentacyclic scaffold, CWO-324 to mimic saframycin A is described. CWO-324 is readily synthesized in five steps from 1,4-diacetyl-piperazine-2,5-dione and 2,5-dimethoxybenzaldehyde. CWO-324 was found to scission DNA, binds to bases 69-83(5′-GCAGTCAGG CACCGT-3′) of Hind III/Rsa I from plasmid pBR322 DNA in a foot-printing study and possesses anti-tumor activity.     

An efficient reagent for the phosphorylation of deoxyribonucleosides, DNA oligonucleotides, and their thermolytic analogues

[reaction: see text] The phosphoramidite 11 was prepared in three steps from methyl 2-mercaptoacetate and demonstrated efficiency in the synthesis of conventional 5'-/3'-phosphate/thiophosphate monoester derivatives of 2'-deoxyribonucleosides and DNA oligonucleotides. Moreover, the use of 11 has enabled the preparation of the dinucleoside phosphorothioate analogue 26 in high yields (>95%) with minimal cleavage (<2%) of the thermolytic thiophosphate protecting group.     

Determination of subnanomolar concentrations of cobalt by adsorptive stripping voltammetry at a bismuth film electrode

Procedures for trace cobalt determinations by adsorptive stripping voltammetry at in situ and ex situ plated bismuth film electrodes are presented. These exploit the enhancement of the cobalt peak obtained by using the Co(II)–dimethylglyoxime–cetyltrimethylammonium bromide–piperazine-N,N-bis(2-ethanesulfonic acid) system. The calibration graph for an accumulation time of 120 s was linear from 2 × 10^–10 to 2 × 10^–8 mol L^–1. The relative standard deviation from five determinations of cobalt at a concentration of 5 × 10^–9 mol L^–1 was 5.2%. The detection limit for an accumulation time of 300 s was 1.8 × 10^–11 mol L^–1. The proposed procedure was applied to cobalt determination in certified reference materials and in tap and river water samples.     

Analytical control of silica glass production. Voltammetric determination of titanium and iron in raw materials and silica glass samples

Adsorptive stripping voltammetric (AdSV) methods are presented for the determination of titanium and iron in quartz and silica glass samples obtained after pressure decomposition. Mandelic acid and catechol were used as complexing agents for titanium and iron, respectively. The method for titanium determination is based on the catalytic effect of chlorate ions. An insoluble residue remaining after decomposition of quartz and silica glass samples in HF+H2SO4 mixture was checked by energy-dispersive X-ray analyses. ET-AAS was applied as a reference method to AdSV measurements.     

Grafting of styrene onto low molecular weight polymers and copolymers of butadiene

The grafting of styrene onto low molecular weight polybutadienes and butadiene–styrene co-polymers was studied. A mathematical method was used for the design of experiments and for the determination of the optimum grafting conditions with respect to the conversion of styrene and the efficiency of grafting. The reaction parameters were temperature (65–105°C), time (2–10 hr), concentration of the initiator, polymer to monomer ratio (10/90–90/10) and dilution by solvent (toluene). The optimum grafting conditions were chosen under which 50–60 wt-% of styrene was grafted onto backbone polymer at a high conversion of the monomer. It was found that the reactions producing graft copolymer prevailed over the styrene homopolymerization when the temperatures employed were lower (65–85°C), and the reaction time (8–10 hr), backbone polymer/monomer ratio, and the dilution by solvent were higher. The efficiency, density, and degree of grafting were found to increase with the increase in the molecular weight of the backbone polymer. The efficiencies and densities of grafting onto low molecular weight polybutedienes were higher than those of grafting onto low molecular weight butadiene–styrene copolymers. Grafting efficiencies and grafting densities were in the ranges 37.8–61.6 wt % and 0.06–0.26, respectively, in the studied range of number-average molecular weights (M?_n = 2400–6000).     

Mechanistic Study on the Oxidation of Promazine and Chlorpromazine by Hexaimidazolcobalt(III) in Acidic Aqueous Media

The kinetics of the oxidation of promazine and chlorpromazine by hexaimidazolcobalt(III) were studied in the presence of a large excess of cobalt(III) and H⁺ ions using u.v.–vis. spectroscopy ([Co^III] = (1–6) × 10⁻³ m, [ptz] = (2.5–10) × 10⁻⁵ m, [H⁺] = 0.05–0.8 m, I = 1.0 m (H⁺, Na⁺, Cl⁻), T = 333–353 K, l = 1 cm). In each case, the reversible reaction leads to formation of cobalt(II) species and a stable cationic radical. A linear dependence of the pseudo-first-order rate constant (k_obs) on [Co^III] with a non-zero intercept was established for both phenothiazine derivatives. A marked difference in the observed reaction rate for promazine and chlorpromazine is associated with the difference in its ability to undergo oxidation and is consistent with a trend in the redox potential changes for these reductants. The activation parameters for reactions studied were determined. Mechanistic consequences of all the results are discussed.