Synthesis and thermal study of rhenium(V) coordination compounds with pyroracemic acid and phenylglyoxylic acid thiosemicarbazones

Rhenium(V) coordination compounds with pyroracemic acid and phenylglyoxylic acid thiosemicarbazones were synthesized for various metal-to-ligand ratios in 1–7 M hydrohalic acids. The composition and structure of the complexes were characterized using a set of physicochemical methods. The thermal stability of rhenium(V) complexes with pyroracemic acid and phenylglyoxylic acid thiosemicarbazones and rhenium(V) solvato complexes with pyroracemic acid thiosemicarbazone was studied thermogravimetrically. The thermolysis mechanism for the complexes was determined as follows: elimination of outer-sphere water, decarboxylation, and dehalogenation.     

腐植酸对砷的吸附作用研究

腐植酸中含有大量的极性基团,对金属离子有较强的吸附性能。运用氢化物-原子荧光光谱法,以泥炭腐植酸为原料,研究了腐植酸对砷(V)离子的吸附作用和腐植酸吸附剂中砷的回收,并得出了最佳的吸附和脱附条件。实验考察了酸度、时间分别对吸附和脱附的影响。结果表明,泥炭腐植酸对砷吸附的最佳模型为Freundlich吸附方程,当溶液成中性时腐植酸对砷的吸附量较大且趋于平稳。砷的浓度为1μg/mL,溶液的pH值为7,吸附时间控制在55min时,吸附效果最佳,最大吸附率为85.49%。脱附的最佳条件为:pH值14,脱附时间20min。     

Individual and simultaneous determination of uric acid and ascorbic acid by flow injection analysis

Flow injection methods for the individual and simultaneous determination of ascorbic acid and uric acid are proposed. A spectrophotometer and a miniamperometric detector are connected in sequence. The calibration graphs for uric acid obtained by measuring its absorbance at 293 nm and its current at +0.6 V are linear up to at least 80 and 70 mug/ml, respectively, with an rsd (n = 10) of 1 % for both methods at mid-range concentrations. The calibration graph for ascorbic acid with amperometric detection is linear up to 80 mg/l. with an rsd (n = 10) of 0.8% at 30 mg/l. The simultaneous determination of uric acid and ascorbic acid is based on measurement of the absorbance of uric acid at 393 nm and amperometric determination of both analytes at +0.6 V. The average relative errors of the analysis of binary mixtures of uric acid and ascorbic acid are 2.2 and 4.2%, respectively.     

Oxidation of malic acid by vanadium (V) in sulphuric acid medium: A kinetic and mechanistic investigation

The oxidation kinetics of malic acid by vanadium(V) in aqueous sulphuric acid was investigated at 303 K by monitoring the appearance of vanadium(IV) at 760 nm. The reaction showed first-order behavior with respect to vanadium(V), malic acid, and hydrogen ion concentration, respectively, regardless of the ionic strength. The reaction rate is enhanced by an increase in ionic strength and a decrease of the dielectric constant of the medium by addition of methanol. The activation parameters were estimated by varying the temperature in the range of 293 K to 313 K to 313 K. An oxidation mechanism is proposed, involving different vanadium(V) species produced in the presence of sulphuric acid. © 1995 John Wiley & Sons, Inc.     

controlled-potential coulometric determination of plutonium with a hydrochloric acid—sulfamic acid electrolyte and phosphate complexing

Total plutonium is selectively determined by a controlled-potential coulometric method in which plutonium is reduced to Pu(III) at 0.25 V (vs. SCE) in a 5.5 M hydrochloric acid—0.015 M sulfamic acid electrolyte, diverse ions are oxidized at 0.57 V, phosphate is added to reduce the Pu(III)—Pu(IV) potential, and Pu(III) is oxidized to Pu(IV) at 0.68 V. None of more than 50 metal ions present in nuclear fuel-cycle material interferes. Many anions are without effect and most interfering ones are removed by preliminary fuming with perchloric acid. The apparatus described consists mainly of commercial components. The relative standard deviation is <0.1% at the 5-mg plutonium level.     

Extraction recovery of vanadium(V) from sulfuric acid solutions

The IR and electronic absorption spectra of di-2-ethylhexyl hydrogen phosphate (HDEHP) extracts of vanadium(V) and sulfuric acid and of vanadium(V) solutions in sulfuric acid were studied. The composition of the extractable complex was determined, and the equation of vanadium(V) extraction with HDEHP was suggested. The equilibrium constant of vanadium(V) extraction from concentrated sulfuric acid solutions was found.     

Vanadium(V) extraction from sulfuric acid solutions

We studied vanadium(V) extraction by di-2-ethylhexylphosphoric acid (DEHPA) from 1.0–12.0 M sulfuric acid. Optimal extraction parameters were determined. IR, ⁵¹V NMR, and electronic spectroscopy was used to determine the stoichiometry of the extracted complex and the reaction equation for vanadium(V) extraction by DEHPA. The equilibrium constant of vanadium(V) extraction by DEHPA was determined.     

胶束扫集毛细管电泳分离测定绿原酸和咖啡酸

采用胶束扫集毛细管电泳分离测定双黄连口服液中的绿原酸和咖啡酸.试验条件为:重力进样时间40 s;以20 mmol/L NaH_2PO_4,100 mmol/L 十二烷基磺酸钠(SDS)为电泳缓冲液(含体积分数15%甲醇,pH 2.20),分离电压-20 kV,检测波长214 nm,讨论了pH、SDS浓度、样品溶剂等对分离效果的影响.在优化条件下,绿原酸和咖啡酸的检出限分别达到1.02和0.168 μg/mL,线性范围分别为5.86～51.5 μg/mL和1.27～14.5 μg/mL.     

电感耦合等离子体-发射光谱分析中硫酸基体效应及抑制

研究了电感耦合等离子体-发射光谱分析中的硫酸基体效应及克服干扰的有效方法。对2%~20%范围内4种不同体积分数H2SO4溶液中30种元素的基体效应进行了观察,发现H2SO4对各元素的谱线发射强度均存在明显的抑制作用。实验证实体积分数5%乙酸可有效抑制H2SO4的基体效应,并建立了H2SO4溶液中痕量元素的电感耦合等离子体-发射光谱分析法。     

Study on stabilities and electrochemical behavior of V(V) electrolyte with acid additives for vanadium redox flow battery

Several acid compounds have been employed as additives of the V(V) electrolyte for vanadium redox flow battery (VRB) to improve its stability and electrochemical activity. Stability of the V(V) electrolyte with and without additives was investigated with ex-situ heating/cooling treatment at a wide temperature range of −5 °C to 60 °C. It was observed that methanesulfonic acid, boric acid, hydrochloric acid, trifluoroacetic acid, polyacrylic acid, oxalic acid, methacrylic acid and phosphotungstic acid could improve the stability of the V(V) electrolyte at a certain range of temperature. Their electrochemical behaviors in the V(V) electrolyte were further studied by cyclic voltammetry (CV), steady state polarization and electrochemical impedance spectroscopy (EIS). The results showed that the electrochemical activity, including the reversibility of electrode reaction, the diffusivity of V(V) species, the polarization resistance and the flexibility of charge transfer for the V(V) electrolyte with these additives were all improved compared with the pristine solution.     

Polymerization of acrylonitrile. Kinetics of the reaction initiated by the vanadium(V)/thioglycollic acid redox system

The polymerization of acrylonitrile initiated by the vanadium(V)-thioglycollic acid redox system has been investigated in aqueous sulphuric acid under nitrogen over the range 30–45°. The polymerization is second order in monomer and first order in thioglycollic acid (TGA). The rate of vanadium(V) disappearance is proportional to (TGA) and [V(V)]. The effects of FeCl₃, CuSO₄ and acetic acid on the polymerization have been investigated. The proposed reaction scheme involves initiation by an organic free radical, produced by the interaction of V(V) with TGA and termination by V(V). Various rate parameters have been evaluated.     

Redox and complexation chemistry of the Cr(VI)/Cr(V)-D-galacturonic acid system

The oxidation of d-galacturonic acid by Cr(VI) yields the aldaric acid and Cr(III) as final products when a 30-times or higher excess of the uronic acid over Cr(VI) is used. The redox reaction involves the formation of intermediate Cr(IV) and Cr(V) species, with Cr(VI) and the two intermediate species reacting with galacturonic acid at comparable rates. The rate of disappearance of Cr(VI), Cr(IV) and Cr(V) depends on pH and [substrate], and the slow reaction step of the Cr(VI) to Cr(III) conversion depends on the reaction conditions. The EPR spectra show that five-coordinate oxo-Cr(V) bischelates are formed at pH < or = 5 with the uronic acid bound to Cr(V) through the carboxylate and the alpha-OH group of the furanose form or the ring oxygen of the pyranose form. Six-coordinated oxo-Cr(V) monochelates are observed as minor species in addition to the major five-coordinated oxo-Cr(V) bischelates only for galacturonic acid : Cr(VI) < or =10 : 1, in 0.25-0.50 M HClO(4). At pH 7.5 the EPR spectra show the formation of a Cr(V) complex where the vic-diol groups of Galur participate in the bonding to Cr(V). At pH 3-5 the Galur-Cr(V) species grow and decay over short periods in a similar way to that observed for [Cr(O)(alpha-hydroxy acid)(2)](-). The lack of chelation at any vic-diolate group of Galur when pH < or = 5 differentiates its ability to stabilise Cr(V) from that of neutral saccharides that form very stable oxo-Cr(V)(diolato)(2) species at pH > 1.     

Extraction of vanadium(V) from acid solutions with octyl alcohol isomers

Vanadium(V) extraction with octyl alcohol isomers from acid solutions was studied. Two areas are determined, wherein the vanadium(V) extraction in relation to acidity of the aqueous phase is maximal. The opposite effects of temperature on the extraction are found. The mechanism of the vanadium(V) extraction with high molecular weight alcohols from weakly acid solutions was suggested.     

Complexes formed in solution between vanadium(IV)/(V) and the cyclic dihydroxamic acid putrebactin or linear suberodihydroxamic acid

An aerobic solution prepared from V(IV) and the cyclic dihydroxamic acid putrebactin (pbH(2)) in 1:1 H(2)O/CH(3)OH at pH = 2 turned from blue to orange and gave a signal in the positive ion electrospray ionization mass spectrometry (ESI-MS) at m/z(obs) 437.0 attributed to the monooxoV(V) species [V(V)O(pb)](+) ([C(16)H(26)N(4)O(7)V](+), m/z(calc) 437.3). A solution prepared as above gave a signal in the (51)V NMR spectrum at δ(V )= -443.3 ppm (VOCl(3), δ(V) = 0 ppm) and was electron paramagnetic resonance silent, consistent with the presence of [V(V)O(pb)](+). The formation of [V(V)O(pb)](+) was invariant of [V(IV)]:[pbH(2)] and of pH values over pH = 2-7. In contrast, an aerobic solution prepared from V(IV) and the linear dihydroxamic acid suberodihydroxamic acid (sbhaH(4)) in 1:1 H(2)O/CH(3)OH at pH values of 2, 5, or 7 gave multiple signals in the positive and negative ion ESI-MS, which were assigned to monomeric or dimeric V(V)- or V(IV)-sbhaH(4) complexes or mixed-valence V(V)/(IV)-sbhaH(4) complexes. The complexity of the V-sbhaH(4) system has been attributed to dimerization (2[V(V)O(sbhaH(2))](+) ? [(V(V)O)(2)(sbhaH(2))(2)](2+)), deprotonation ([V(V)O(sbhaH(2))](+) - H(+) ? [V(V)O(sbhaH)](0)), and oxidation ([V(IV)O(sbhaH(2))](0) -e(-) ? [V(V)O(sbhaH(2))](+)) phenomena and could be described as the sum of two pH-dependent vectors, the first comprising the deprotonation of hydroxamate (low pH) to hydroximate (high pH) and the second comprising the oxidation of V(IV) (low pH) to V(V) (high pH). Macrocyclic pbH(2) was preorganized to form [V(V)O(pb)](+), which would provide an entropy-based increase in its thermodynamic stability compared to V(V)-sbhaH(4) complexes. The half-wave potentials from solutions of [V(IV)]:[pbH(2)] (1:1) or [V(IV)]:[sbhaH(4)] (1:2) at pH = 2 were E(1/2) -335 or -352 mV, respectively, which differed from the expected trend (E(1/2) [VO(pb)](+/0) < V(V/IV)-sbhaH(4)). The complex solution speciation of the V(V)/(IV)-sbhaH(4) system prevented the determination of half-wave potentials for single species. The characterization of [V(V)O(pb)](+) expands the small family of documented V-siderophore complexes relevant to understanding V transport and assimilation in the biosphere.     

Oxovanadium complex as potential nucleic acid binder

DNA binding study of a vanadium(V) complex, Oxo-chloro-bis-N-phenylbenzohydroxamto-vanadium(V), derived from N-phenylbenzohydroxamic acid(PBHA) form a violet color complex with vanadium (V) in presence of hydrochloric acid is performed using absorption, fluorescence and viscometric techniques. The binding parameters of the PBHA-V(V) complex using calf thymus DNA (ct-DNA) and torula yeast RNA (t-RNA) have been determined. The complex shows the ability of cooperatively minor groove binding with ct-DNA as indicated by remarkable hyperchromicity and a blue shift of the absorption spectra. Quenching of metal complex calculation was carried out with Stern-Volmer equation and K_sv was found to be 2.32 ± 0.18 × 10⁴ M^?1, while in the case of t-RNA, enhancement is observed and that means the compound was not able to displace the Ethidium Bromide(EB)-t-RNA complex. Molecular docking was also applied to predict the mode of interaction of the hydroxamic acid with ct-DNA and t-RNA. DNA binding results of the complex are compared with those of the parent ligand.     

Electrically controlled separation of maleic acid and fumaric acid through a poly(vinyl alcohol)/poly(acrylic acid) composite membrane

The separation of maleic acid (MA) from a mixture of MA and fumaric acid (FA) was studied using an electrically activated polyelectrolyte gel membrane. The membrane was prepared through the iterative freezing-thawing of an aqueous solution containing poly(vinyl alcohol) and poly(acrylic acid). The separation of MA from an equimolar mixture (5 mM) of MA and FA using the membrane was performed under different conditions of pH (1–8) and electric fields (2–6 V). It was found that MA was separated from the mixture at pH 2 under an applied electric field of greater than 2 V because only the COOH groups of MA were dissociated at pH 2 and the MA⁻ ions were transported through the membrane toward the electrode opposite in sign to their charge.     

Citric acid oxidation by vanadium(V) in sulfuric acid medium: Kinetic and mechanistic study

The citric acid oxidation by vanadium(V) in sulfuric acid medium at 303 K is reported. The reaction rate was determined spectrophotometrically by monitoring the formation of vanadium(IV) at 760 nm. The oxidation showed a first‐order dependence with respect to vanadium(V) concentration and fractional order with respect to citric acid concentrations, with no control and with constant ionic strength. The reaction is also first order with respect to sulfuric acid concentration with no control and of fractional order at constant ionic strength. The reaction rate is enhanced by an increase of ionic strength and increased by a decrease of the dielectric constant. The activation parameters were calculated based on the rate constants determined in the 293 to 313 K interval. The proposed oxidation mechanisms and the derived rate laws are consistent with the experimental rate laws. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 566–572, 2000     

Simultaneous detection of epinephrine,uric acid,and ascorbic acid with graphene-modified electrode

A graphene-modified glassy carbon electrode was obtained via drop-casting method and applied to the simultaneous detection of epinephrine, uric acid, and ascorbic acid by cyclic voltammetry in a phosphate buffer solution (pH 3.0). The oxidation potentials of epinephrine, uric acid, and ascorbic acid were 0.484, 0.650, and 0.184 V at the graphene-modified glassy carbon electrode, respectively. The peak separation between epinephrine Pand uric acid, epinephrine and ascorbic acid, and uric acid and ascorbic acid was about 166, 300, and 466 mV, respectively. So, this graphene-modified electrode can be used for simultaneous determination of each component in a mixture.     

Kinetic and mechanistic aspects for the tartaric acid oxidation by vanadium(V) in sulfuric acid medium

Tartaric acid oxidation by vanadium(V) in sulfuric acid medium was investigated spectrophotometrically at 760 nm and 30°C by appearance of the vanadium(IV), as vanadyl. The reaction rate was determined under pseudo-first-order conditions with an excess of hydroxyacid over the oxidant concentration. The oxidation showed a first-order dependence with respect to vanadium(V) concentration and fractional orders with respect to tartaric acid and sulfuric acid concentrations, with no control and with constant ionic strength. The reaction rate is enhanced by an increase of ionic strength, and slightly reduced by a decrease of the dielectric constant of the medium. The activation parameters were calculated based on the rate constants determined in the 293 to 313 K interval. The proposed oxidation mechanisms and the derived rate laws are consistent with the experimental rate laws. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 55–61, 1998.     

The chromic acid oxidation of oxalic acid : Evidence of chromium(IV) oxidation

In the chromic acid oxidation of oxalic acid in the range where the reaction is first order in the substrate, oxalic acid is very reactive toward chromium(IV) and rather unreactive toward chromium(V). A mechanism analogous to that of the chromic acid oxidation of alcohols and aldehydes is proposed for the first order kinetic term.