Iodine cyanide as volumetric oxidant

Iodine cyanide has been developed as an oxidant for the determination of iodide, sulphite, thiosulphate, thiocyanate, arsenic (III), antimony(III), tin(II), mercury(I), iron(II), ascorbic acid and beta-naphthol in dilute aqueous mineral acids, glacial acetic acid and 1:1 acetic acid-acetic anhydride mixture, with visual and potentiometric methods of end-point detection.     

alpha-(Phenylazo)-4-nitrobenzyl cyanide, a new acid-base indicator

A new acid-base indicator, alpha-(phenylazo)-4-nitrobenzyl cyanide, is proposed. The indicator changes colour from yellow to violet in the presence of alkali owing to the formation of a nitronic acid structure. This indicator is applicable for the titration of weak acids in acetone and ethanol media or in a mixture of these organic solvents and water, with 0.1M aqueous sodium hydroxide as titrant. The absorption spectra have been recorded for the indicator in 25%, 50% and 75% aqueous ethanol and acetone. By means of the spectra the dissociation constants in these media have been determined. The pK value of alpha-(phenylazo)-4-nitrobenzyl cyanide is 12.10 in water, and is decreased considerably in acetone but only slightly in ethanol. This behaviour is similar to that of positively charged weak acids and irregular for a weak acid carrying no charge or a negative charge.     

Cation-exchange behaviour of several elements in nitric acid-organic solvent media

The cation-exchange behaviour of 19 elements towards the strongly acidic cation-exchange resin Dowex 50-X8 in media containing varying concentrations of organic solvents and aqueous nitric acid is reported. Based on the determination of the distribution coefficients of these elements in the organic solvents methanol, ethanol, n-propanol, isopropanol, methyl glycol, acetone, tetrahydrofuran and acetic acid, the conditions most suitable for their quantitative separation are indicated and discussed.     

Iodine--iodide reference electrode for potentiometric titrations of bases in acetic acid

The suitability of the half-cell Pt/I2, KI in glacial acetic acid as reference electrode for potentiometric titrations of weak bases in the same medium was investigated. This electrode is easily prepared. It has been found very convenient in use and performing at least as well as the best electrodes used for the same purpose. Some phenomenological aspects of the behaviour of the above half-cell, of interest for the use as the reference electrode in the laboratory practice have been observed, that show important differences respect aqueous medium and other organic solvents.     

Ammonium boranes for the selective complexation of cyanide or fluoride ions in water

With the recognition of aqueous fluoride and cyanide ions as an objective, we have investigated the anion binding properties of two isomeric ammonium boranes, namely [p-(Mes2B)C6H4(NMe3)]+ ([1]+) and [o-(Mes2B)C6H4(NMe3)]+ ([2]+). These cationic boranes, which could be obtained by reaction of the known 4- and 2-dimesitylboryl-N,N-dimethylaniline with MeOTf, have been investigated both experimentally and computationally. They both react with fluoride and cyanide ions in organic solvents to afford the corresponding fluoroborate/ or cyanoborate/ammonium zwitterions 1F, 1CN, 2F, and 2CN. In aqueous solution, however, these cationic boranes behave as remarkably selective receptors. Indeed, [1]+ only complexes cyanide ions while [2]+ only complexes fluoride ions. In H2O/DMSO 60:40 vol (HEPES 6 mM, pH 7), the cyanide binding constant of [1]+ and the fluoride binding constant of [2]+ are respectively equal to 3.9 (+/-0.1) x 108 and 910 (+/-50) M-1. Structural and computational studies indicate that both steric and electronic effects contribute to the unusual selectivity displayed by these cationic boranes. Owing to favorable Coulombic effects, the para-derivative [1]+ has a very high affinity for cyanide; yet these effects are not sufficiently intense to allow complexation of the more efficiently hydrated and less basic fluoride anion. In the case of the ortho-derivative [2]+, the proximity of the ammonium moiety leads to an increase in the Lewis acidity of the boron center thus making fluoride binding possible. However, steric effects prevent cyanide coordination to the boron center of [2]+. Finally, cation [1]+ and [2]+ bind their dedicated anions reversibly and show a negligible response in the presence of other common anions including Cl-, Br-, I-, NO3-, OAc-, H2PO4-, and HSO4-.     

Anion-exchange behaviour of several elements in hydrobromic acid-organic solvent media

The anion-exchange behaviour of 19 elements in hydrobromic acid-organic solvent media has been investigated. The batch distribution coefficients of the metal ions were determined in these systems employing the strongly basic anion-exchange resin Dowex 1, x 8. Organic solvents used were methanol, ethanol, n-propanol, isopropanol, methyl glycol, acetone, tetrahydrofuran and acetic acid. The most suitable conditions for some quantitative separations based on these equilibrium studies are indicated and discussed.     

Extraction of group VIII elements with 1-phenyl-3-methyl-4-trifluoroacetyl-pyrazolone-5

The extraction of group VIII elements with 1-phenyl-3-methyl-4-trifluoracetyl-pyrazolone-5 from aqueous solutions in chloroform has been studied as a function of pH. Fe(III), Ni(II), Pd(II) and Rh(III) show partial extraction whereas Co(II) is extracted quantitatively. The effect of citrate, cyanide, fluoride, iodide, thiosulphate and thiourea on the extraction of metal ions has been investigated. Back-extraction studies were carried out to strip metal ions from organic phase into appropriate aqueous solutions. Based on these findings some useful analytical separations have been proposed and a few of their possible applications have been discussed.     

Thermosolvatochromism of merocyanine polarity indicators in pure and aqueous solvents: relevance of solvent lipophilicity

The following novel solvatochromic probes were synthesized: 2,6-dibromo-4-[(E)-2-(1-alkylpyridinium-4-yl)ethenyl] phenolate, where the alkyl groups are methyl, n-butyl, n-hexyl, and n-octyl, respectively. Solvatochromism of three of these probes (C(1), C(4), and C(8)) was studied in 36 protic and aprotic solvents. A modified linear solvation energy relationship has been applied to the data obtained at 25 degrees C. Correlation of (empirical) polarities with other solvent properties showed more dependence on lipophilicity than on basicity. A similar conclusion has been reached for a series of other solvatochromic indicators. Exceptions are those that carry acidic hydrogens, being biased toward solvent basicity. Thermosolvatochromism has been studied in mixtures of water with methanol, 1-propanol, acetonitrile, and DMSO. Thermosolvatochromic data have been treated according to a model that explicitly considers the presence in bulk solution of three "species": water, organic component, and solvent-water hydrogen-bonded aggregate. Solvation by the latter is favored over solvation by either of the two precursor solvents (aqueous DMSO is an exception). Temperature increase resulted in desolvation of the probes, due to concomitant decrease of the structures of the component solvents. The above-mentioned modified solvation equation has been successfully applied to solvatochromism in aqueous methanol and aqueous 1-propanol.     

Catalytic asymmetric synthesis of O-acetyl cyanohydrins from KCN,Ac2O and aldehydes

A (salen)titanium catalyst has been found to induce the asymmetric addition of potassium cyanide and acetic anhydride to aldehydes, giving enantiomerically enriched cyanohydrin esters with up to 92% enantiomeric excess using just 1 mol% of the catalyst. This is the first report of the asymmetric synthesis of cyanohydrin derivatives using a cyanide source which is non-volatile and inexpensive.     

Solvent extraction of gold(III) with 1-phenyl-3-methyl-4-trifluoroacetylpyrazolone-5

A simple, rapid and selective separation procedure of gold based on its extraction with 1-phenyl-3-methyl-4-trifluoroacetylpyrazolone-5 has been developed. The dependence of the distribution ratio of gold on the pH of aqueous solutions, concentration of hydrochloric, nitric and perchloric acids and the organic solvents has been investigated. Decontamination factors for a number of metal ions with respect to gold are reported. Excellent separation of gold is obtained from many elements including noble metals. Citrate, cyanide, iodide, thiosulfate and thiourea completely mask gold, whereas oxalate does not interfere. Solutions of 1 M HCl, 0.2 M KCN, and the buffer of pH 0.8 readily strip gold from the organic phase. Some useful analytical applications of this procedure are discussed.     

四磺酸基酞菁锌在水和非水溶剂中的电化学性质研究

在非水溶剂（二甲基亚砜（ＤＭＳＯ）及Ｎ,Ｎ＿二甲基甲酰胺（ＤＭＦ））中的伏安曲线．呈现三对电流峰,表明存在三个可逆或准可逆酞菁配体的单电子转移过程,而在水溶液中则不呈现准可逆行为,且波形改变很大．此外,还比较了四磺酸基酞菁锌的水溶液在自然光和红光（６００～７００ｎｍ）照射下的循环伏安曲线,其氧化还原峰的数目和峰电位基本不变,但在红光照射下比自然光照射下的峰电流明显增大．     

Utility of 1-octanol/octane mixed solvents for the solvent extraction of aluminum(III), gallium(III), and indium(III) with 8-quinolinol.

Using 1-octanol/octane mixed solvents, the extraction of aluminum(III), gallium(III) and indium(III) with 8-quinolinol was carried out at 25 degrees C. The formation constants of the respective metal(III) 8-quinolinolates in the aqueous phase and their partition constants between the mixed solvents and water were determined based on an analysis of the extraction equilibria. The relationship between the partition constants of 8-quinolinol and its complexes was analyzed by the regular solution theory. The molar volumes of aluminum(III), gallium(III) and indium(III) 8-quinolinolates, calculated from the present results, suggest that the electrostriction effect functions in complex forming. It has been found that octane/1-octanol mixed solvents were available not only for the extraction of metal ions, but also for determining the formation constants of these metal 8-quinolinolates in the aqueous phase and their partition constants.     

The solvent extraction of flurazepam and its major metaboutes and their determination by polarography

The solvent extraction of flurazepam and its major metabolites from aqueous solutions of varying pH has been studied at concentrations encountered in body fluids following therapeutic dosage. Distribution ratios have been calculated over the pH range 0–14 and for the solvents, ethyl acetate, diethyl ether, cyclohexane and petroleum ether (40–60°C). Based on this study, a solvent extraction scheme is evaluated for the recovery of such concentrations of these compounds in mixtures, with final polarographic determinations. Recoveries exceeding 95% were found; the method is specific for the determination of flurazepam and its acetic acid metabolite in mixtures. The total concentration of the remaining metabolites, i.e. the hydroxyethyl-, N-1-desalkyl-, and N-1-desalkyl-3-hydroxy metabolites can be estimated after solvent extraction and differential pulse polarography in alkaline solutions.     

Chromatographic behaviour of alkaloids on thin layers of cation exchangers. II. Alginic acid, Rexyn 102, Dowex 50-X4 and CMCNa.

The chromatographic behaviour of 48 alkaloids on cation exchangers with cellulose, paraffin and polystyrene matrices in both the acid and sodium salt forms has been investigated. Water-organic solvent mixtures, aqueous buffer solutions and organic and mineral acid solutions in both water and in aqueous-organic solvents have been used as eluents. The retention mechanisms of these compounds on alginic acid, Rexyn 102 (Hplus) and Dowex 50-X4 (Hplus) thin layers are discussed. Interesting separations of the alkaloids were carried out on alginic acid and Rexyn 102 (Hplus).     

新的液晶性壳聚糖衍生物——氰乙基壳聚糖的合成与表征

甲壳素是自然界蕴藏量最丰富的天然高分子化合物之一,但人们对它的了解却远不如纤维素和淀粉.仅就液晶领域而言,纤维素衍生物的液晶性早已为人们所认识,例如氰乙基纤维素的液晶性已有很多研究.     

Solvent and salt effects on the redox behaviour of trisacetylacetonato manganese(III)

The polarographic and voltammetric behaviour of trisacetylacetonato manganese(III) [Mn(acac)₃] has been studied in methanol, ethanol, tetrahydrofurane, butyrolactone, propylenecarbonate, N,N-dimethylformamide, acetonitrile, nitromethane, N-methylpyrrolidone(2), 1,2-dichloroethane, dichloromethane, dimethylsulfoxide and acetic acid, Mn(acac)₃ was found to undergo a reversible one-electron reduction to Mn(acac)₃^? in most of the solvents mentioned. A further reduction at very negative potentials has been also observed in several solvents. The oxidation of Mn(acac)₃ to Mn(acac)₃⁺ has been studied by cyclovoltammetry in dichloromethane, nitromethane, acetonitrile, propylenecarbonate, N-methylpyrrolidinone(2), N,N-dimethylformamide and dimethylsulfoxide. The polarographic behaviour of NaMn(acac)₃ and Mn(acac)₂ has been investigated in the seven solvents listed above as well as in methanol. The half-wave potentials and the peak potentials referred to bisbiphenylchromium(I)/bisbiphenylchromium(0) as a reference redox system were found to vary with the nature of the solvent. Conductivity studies of Mn(acac)₃ and NaMn(acac)₃ have been carried out in these solvents. U.v.-visible and near i.r. spectra have been recorded of Mn(acac)₃, NaMn(acac)₃, Mn(acac)₂ and Na(acac) in the solvents mentioned. It has further been observed that the half-wave potentials for the polarographic reduction of Mn(acac)₃ shifted to more positive values by the addition of alkali metal ions and to more negative values by the addition of halide ions. The interactions of the solvent with Mn(acac)₃ and the variation of redox potentials with both the solvent and the added electrolytes will be discussed.     

STUDIES ON FLAVINS IN ORGANIC SOLVENTS—II*. PHOTODECOMPOSITION OF RIBOFLAVIN IN THE PRESENCE OF OXYGEN

Abstract— The photodegradation of riboflavin by 436 mμ monochromatic light and of lumichrome by white nonfiltered light was studied in a set of organic solvents including ethanol, acetone, dioxane, pyridine and acetic acid. For comparison, water was used as a solvent. Photolysis was carried out in the presence of atmospheric oxygen. Riboflavin and lumichrome were found to be effectively stabilized towards the action of light by hydrogen bonds with solvent molecules, and consequently are most light-stable in water solutions. The overall scheme of riboflavin photolysis in organic solvents seems to be the same as in aqueous solutions. Lumichrome has been found as the main product of riboflavin photolysis in the organic solvents tested.     

A rapid responsive and highly selective probe for cyanide in the aqueous environment

A colorimetric and fluorescent cyanide probe based on 7-(trifluoroacetamino)coumarin has been prepared. This structurally simple probe displays rapid response and high selectivity for cyanide over other common anions in the aqueous solution. The sensing of cyanide was performed via the nucleophilic attack of cyanide anion to carbonyl of the probe with a 1:1 binding stoichiometry, which could be confirmed by Job’s plot, ¹H NMR, and MS studies. DFT/TDDFT calculations support that the fluorescence enhancement of the probe is mainly due to the ICT process improvement. The detection limit of the fluorescent assay for cyanide is as low as 0.3 μM in a rapid response of less than 30 s. Thus, the present probe should be applicable as a practical system for the monitoring of cyanide concentrations in aqueous samples.     

Mixed aqueous solutions as dilution media in the determination of residual solvents by static headspace gas chromatography

Static headspace (HS) sampling has been commonly used to test for volatile organic chemicals, usually referred to as residual solvents (RS) in pharmaceuticals. If the sample is not soluble in water, organic solvents are used. However, these seriously reduce the sensitivity in the determination of some RS. Here, mixed aqueous dilution media (a mixture of water and an organic solvent like dimethyl formamide, dimethyl sulfoxide or dimethyl acetamide) were studied as alternative media for static HS-gas chromatographic analysis. Although it has been known that mixed aqueous dilution media can often improve sensitivity for many RS, this study used a systematic approach to investigate phase volumes and the organic content in the HS sampling media. Reference solutions using 18 different class 1, 2 and 3 RS were evaluated. The effect of salt addition was also studied in this work. A significant increase in the peak area was observed for all RS using mixed aqueous dilution media, when compared with organic solvents alone. Matrix effects related to the mixed aqueous dilution media were also investigated and reported. Repeatability and linearity obtained with mixed aqueous dilution media were found to be similar to those observed with pure organic solvents.     

Effects of solvents on the electron configurations of the low-spin dicyano[meso-tetrakis(2,4,6-triethylphenyl)porphyrinato]iron(III) complex: importance of the C-H...N weak hydrogen bonding

There are two types of electron configurations, (d(xy))(2)(d(xz), d(yz))(3) and (d(xz), d(yz))(4)(d(xy))(1), in low-spin iron(III) porphyrin complexes. To reveal the solvent effects on the ground-state electron configurations, we have examined the (13)C- and (1)H-NMR spectra of low-spin dicyano[meso-tetrakis(2,4,6-triethylphenyl)porphyrinato]ferrate(III) in a variety of solvents, including protic, dipolar aprotic, and nonpolar solvents. On the basis of the NMR study, we have reached the following conclusions: (i) the complex adopts the ground state with the (d(xz), d(yz))(4)(d(xy))(1) electron configuration, the (d(xz), d(yz))(4)(d(xy)())(1) ground state, in methanol, because the d(pi) orbitals are stabilized due to the O-H...N hydrogen bonding between the coordinated cyanide and methanol; (ii) the complex also exhibits the (d(xz), d(yz))(4)(d(xy))(1) ground state in nonpolar solvents, such as chloroform and dichloromethane, which is ascribed to the stabilization of the d(pi) orbitals due to the C-H...N weak hydrogen bonding between the coordinated cyanide and the solvent molecules; (iii) the complex favors the (d(xz), d(yz))(4)(d(xy))(1) ground state in dipolar aprotic solvents, such as DMF, DMSO, and acetone, though the (d(xz), d(yz))(4)(d(xy))(1) character is less than that in chloroform and dichloromethane; (iv) the complex adopts the (d(xy))(2)(d(xz), d(yz))(3) ground state in nonpolar solvents, such as toluene, benzene, and tetrachloromethane, because of the lack of hydrogen bonding in these solvents; (v) acetonitrile behaves like nonpolar solvents, such as toluene, benzene, and tetrachloromethane, though it is classified as a dipolar aprotic solvent. Although the NMR results have been interpreted in terms of the solvent effects on the ordering of the d(xy) and d(pi) orbitals, they could also be interpreted in terms of the solvent effects on the population ratios of two isomers with different electron configurations. In fact, we have observed the unprecedented EPR spectra at 4.2 K which contain both the axial- and large g(max)-type signals in some solvents such as benzene, toluene, and acetonitrile. The observation of the two types of signals has been ascribed to the slow interconversion on the EPR time scale at 4.2 K between the ruffled complex with the (d(xz), d(yz))(4)(d(xy))(1) ground state and, possibly, the planar (or nearly planar) complex with the (d(xy))(2)(d(xz), d(yz))(3) ground state.