Oxidative degradation studies of an oxazolidinone-derived antibacterial agent,RWJ416457, in aqueous solutions

The rates of oxidative degradation of a new antibacterial drug, RWJ416457, in aqueous solutions were investigated over the pH-range of 2 to 10. Two oxidative degradates were identified and the influences of pH, buffer concentration, metal ions, metal chelating agents, and temperatures were studied. The pH, metal chelating agents, and metal ions significantly changed the product distribution in addition to the degradation rate. Oxidative degradation is believed to follow a hydrogen abstraction (HAT) pathway. One degradate was the major product under acidic conditions and its predominance is attributed to a resonance-stabilized intermediate. The importance of the resonance structure was diminished under neutral and basic conditions. The product distribution changed and two degradates were formed in equal amounts. The study results guided the formulation development to minimize oxidation.     

Speciation, selective extraction and preconcentration of chromium ions via alumina-functionalized-isatin-thiosemicarbazone

A method is presented and described for speciation, extraction and preconcentration of Cr(III) and Cr(VI) based on dynamic and static solid phase extraction techniques. Three newly designed alumina phases-physically adsorbed-isatin-thiosemicarbazone (I-III) were synthesized, characterized, tested for stability and applied as inorganic ion exchangers and chelating solid sorbents for various metal ions. The selectivity characteristics incorporated into these alumina phases were studied and evaluated via determination of the distribution coefficients and separation factors of chromium species versus other interacting metal ions. Quantitative recovery of Cr(VI) was accomplished by alumina phases (I-III) in pH 1.0 giving percentage extraction values of approximately 99.9-100.0%, while Cr(III) was found to be quantitatively recovered by these sorbents in pH 7.0 leading to percentage extraction values approximately 100.0% with minimal or no interference between these two species under the studied buffering conditions. Selective solid phase speciation and preconcentration of Cr(III) and Cr(VI) in various real water samples were successfully performed and accomplished by newly designed alumina phases (I-III) via a preconcentration micro-column.     

Effect of various chelating agents on supercritical carbon dioxide extraction of indium(III) ions from acidic aqueous solution

Indium and its compounds have numerous industrial applications in the manufacture of liquid crystal displays and semiconductors. Indium compounds are considered hazardous materials that can be carcinogenic. Supercritical fluid extraction using carbon dioxide was utilized in this research as a sample pretreatment step for extraction of indium(III) ions from the synthetic etching wastewater of the semiconductor and optoelectronic industries. Several parameters, including various chelating agents, pH of solution, molar ratio of chelating agent to indium(III) ions, temperature and pressure were systematically investigated. Indium(III) ions were extracted by supercritical CO2 combined with several various types of chelating agents including beta-diketone (AcAcH), fluorinated beta-diketone (TTAH), thiopyridine (PySH), and piperidinyldithiocarbamic acid (NCS2H) to extract the ions from acidic aqueous solution. The performance of the various chelating agents from different studies indicated that the extraction efficiency by the supercritical CO2 was in the order: NCS2H>or==PySH>TTAH>AcAcH. The optimum pH for supercritical CO2 extraction should fall in the range from 2.0 to 3.0. The optimum molar ratio of chelating agents to indium(III) ions was found to be a ratio of 10:1. It was also revealed that the optimal extraction pressure and temperature for the supercritical CO2 extraction of indium(III) with various chelating agents AcAcH, PySH and NCS2H were 70 degrees C 2000 psi, 60 degrees C 2000 psi, and 60 degrees C 2000 psi, respectively.     

Preparation of pure superconductors from polymer chelate YBa2Cu3O7-x precursors using poly[(N, N-dicarboxymethyl)allylamine]

Bulk Yba₂Cu₃O_7-x (YBCO) was prepared by a polymer chelate precursor method using poly[(N,N-dicarboxymethyl)allylamine] (PDAA) as a chelating polymer. An aqueous solution containing PDAA and 1/2 or 1/4 equivalent molar amount of metal nitrates (Y : Ba : Cu=1 : 2 : 3) to the repeating unit of PDAA at pH 8 was poured into ethanol to precipitate the polymer-metal chelate precursor. The precursor containing 1/2 equivalent molar amount of metal ions was calcined at 880°C for 10 h, sintered at 920°C for 2 h, and annealed at 600°C for 5 h. The product exhibited a pure superconducting orthorhombic phase. However, the precursor containing 1/4 equivalent molar amount of metal ions gave a mixture of orthorhombic and tetragonal phases under the same conditions. The influence of a purification process for PDAA on the preparation of YBCO was also examined. The electrical resistance and susceptibility of the YBCO sample prepared by optimum conditions were measured. The sintered sample showed superconductivity with T_c (onset) at 93 K and T_c (end) at 91 K. The narrow superconducting transition demonstrated here is attributed to the high purity and homogeneity of the sample prepared from optimized polymer chelate precursor technique. This revised version was published online in November 2006 with corrections to the Cover Date.     

Oxidation of triclosan by ferrate: reaction kinetics, products identification and toxicity evaluation

The Crystal Violet (CV) dye represented one of the major triphenylmethane dyes used in textile-processing and some other industrial processes. Various metals doped titanium dioxide (TiO(2)) photocatalysts have been studied intensively for the photodegradation of dye in wastewater treatment. In order to understand the mechanistic detail of the metal dosage on the activities enhancement of the TiO(2) based photocatalyst, this study investigated the CV photodegradation reactions under UV light irradiation using a Pt modified TiO(2) photocatalyst. The results showed that Pt-TiO(2) with 5.8% (W/W) Pt dosage yielded optimum photocatalytic activity. Also the effect of pH value on the CV degradation was well assessed for their product distributions. The degradation products and intermediates were separated and characterized by HPLC-ESI-MS and GC-MS techniques. The results indicated that both the N-de-methylation reaction and the oxidative cleavage reaction of conjugated chromophore structure occurred, but with significantly different intermediates distribution implying that Pt doped TiO(2) facilitate different degradation pathways compared to the P25-TiO(2) system.     

Recovery of nickel and cobalt from organic acid complexes: adsorption mechanisms of metal-organic complexes onto aminophosphonate chelating resin

This study examined the recovery of nickel and cobalt from organic acid complexes using a chelating aminophosphonate Purolite S950 resin. These metal complexes are generated by bioleaching nickel laterite ores, a commercial nickel and cobalt mineral oxide, with heterotrophic organism and their metabolites or organic acid products. Equilibrium adsorption tests were conducted as a function of Ni and Co concentrations (15-2000 mg/L), solution pH (0.01 and 0.1 M acids) and three metabolic complexing agents (citrate, malate and lactate). It was shown that the adsorption of the various Ni- and Co-complexes on Purolite were quite low, 16-18 and 5.4-9 mg/g of resin, respectively, in comparison to the smaller nickel ions and nickel sulfate. This was attributed to the bulky organic ligands which promoted crowding effect or steric hindrance. The adsorption of these complexes was further hampered by the strong affinity of the resin to H+ ions under acidic conditions. Mechanisms of adsorption, as inferred from the fitted empirical Langmuir and Freundlich models, were correlated to the proposed steric hindrance and competitive adsorption effects. Nickel and cobalt elution from the resin were found be effective and were independent of the type of metal complexes and metal concentrations. This study demonstrated the relative challenges involved in recovering nickel and cobalt from bioleaching solutions.     

Synthesis of β-cyclodextrin functionalized gold nanoparticles for the selective detection of Pb2+ ions from aqueous solution

In the present study we carried out the synthesis of β-cyclodextrin (β-CD) functionalized gold nanoparticles (AuNPs) using a microwave assisted heating method in alkaline media. Stable dispersion of β-CD stabilized AuNPs was obtained at an optimized pH of 10.5. At this pH value the deprotonated secondary hydroxyl group of β-CD shows the highest chelating affinity toward Pb²⁺ ions thereby inducing AuNP aggregation. The Pb²⁺ induced aggregation in β-CD-AuNP solution is monitored by both colorimetric response and UV-Vis spectroscopy. TEM, DLS and FTIR analyses were carried out to confirm the Pb²⁺ ion induced aggregation behaviour of β-CD-AuNPs under alkaline conditions. Furthermore at the experimental pH the response of the β-CD-AuNP system towards Pb²⁺ ions is selective when compared with other interfering metal cations.     

Heavy metal stabilization in municipal solid waste incineration flyash using heavy metal chelating agents

Heavy metal chemical stabilization with synthesized heavy metal chelating agent was assessed for flyash from municipal solid waste incinerator. Flyash can contain heavy metals (e.g. Pb, Cd) which can leach. A new kind of heavy metal chelating agent showed more attractive competition than inorganic chemicals in stabilizing flyash. The synthesizing method of this kind of heavy metal chelating agent was explained in this paper, and the technology process and treatment efficiency of the chelating agent in treating flyash were experimentally studied, which was compared with the results of inorganic chemical agents such as sodium sulfide and lime. The heavy metals in flyash were stabilized more effectively by using heavy metal chelating agents than by using sodium sulfide and lime, furthermore, the stabilized products using the chelating agents can meet the landfill disposal controlling standards for heavy metal waste. pH-dependent leaching experiment showed the stabilized flyash by treatment with heavy metal chelating agent could keep long-term stabilization within a broad range of pH value. Thus, the risk of secondary pollution for the stabilized products was reduced dramatically when the environment condition changes during its disposal period.     

Dynamics of iron release from transferrin N-lobe studied by electrospray ionization mass spectrometry

Transferrins constitute a class of metalloproteins that are involved in circulatory iron transport in a variety of species. The metal ion-binding properties of these proteins have been the focus of extensive research efforts in the past decade due to their extreme importance in a variety of biological and healthcare-related fields. The large size of these proteins, as well as the presence of high-spin metal ions (e.g., Fe3+), limits the use of NMR. In this work, we report on the use of electrospray ionization mass spectrometry (ESI MS) to study dynamics of the transferrin system in vitro under conditions that are designed to mimic the endosomal environment. ESI MS is shown to provide valuable insights into the mechanistic aspects of metal ion-binding/release by transferrins and is complementary to other spectroscopic techniques. Conformational stability of the complex is evaluated based on the appearance of the charge-state distribution of protein ions, while the composition of the protein-ligand complex is determined based on the mass of the protein ions. In the absence of iron chelators, a stepwise dissociation of the ternary complex (protein-metal ion-synergistic anion) is observed as the solution pH is gradually decreased. Although the release of synergistic anion from the complex is initiated at typical endosomal pH levels (i.e., 5.5), metal ion remains largely bound to the protein until the pH is lowered to a level of approximately 4.5. Under these conditions, a significant fraction of the protein populates unfolded conformations. In stark contrast to this behavior, addition of an iron chelating agent (citrate) to the protein solution results in facile iron release at typical endosomal pH levels without any detectable unfolding of the protein. The mass spectral data lends further credibility to the notion that the holoprotein samples conformations that are specific to the apo form (e.g., "open conformation"), from which iron dissociation most likely occurs. The results of the present study demonstrate that ESI MS can be used to model metal ion release from transferrin under conditions that are designed to mimic the physiological environment.     

Effect of different organic additives on the shape,size and scintillation properties of Bi4Ge3O12 powders synthesized by the microwave-hydrothermal method

A route for production of fine Bi₄Ge₃O₁₂ (BGO) powder is sought after to lower the cost of scintillation devices and make their shapes more versatile. A systematic study of highly dispersed BGO crystallization under the hydrothermal-microwave (HTMW) conditions was carried out in the present work. Anionic, cationic and non-ionic surfactants, chelating agents and polyols were used to modify the synthesis and their respective effects on phase composition and morphology were determined. It was shown that chelating agents or other additives that are capable of forming complexes with the bismuth ions allow the production of smaller, non-aggregated particles and have the procedure be scaleable. BGO powders of various morphology were synthesized and study of the optical properties of the product discovered their advantages over traditional single-crystal material. The BGO powders obtained in optimal HTMW conditions are characterized by the presence of a single intense fast scintillation component with a flash time of about 11 ns which is by an order of magnitude less than that observed in single-crystal BGO (327 ns). This suggests the suitability of these powders for the production of scintillation materials with improved properties. This material is promising for creating highly sensitive composite detectors with a high rate of counting events.     

Adsorption mechanism of trivalent metal ions on chelating resins containing iminodiacetic Acid groups with reference to selectivity

The adsorption equilibria of seven trivalent metal ions (M(3+): Sc(3+), Y(3+), La(3+), Fe(3+), Al(3+), Ga(3+), and In(3+)) on chelating resins containing iminodiacetic acid groups (-LH(2)) were studied. Adsorption curves, measured under the conditions of metal ions in excess against chelating groups, directly indicated the metal-to-ligand ratio of the complexes formed in the resin phase. Iron and group 13 metal ions were adsorbed as (-L)(2)HM, while group 3 metal ions were adsorbed as (-L)(3)H(3)M and (-L)(2)HM. The adsorption constants for (-L)(2)HM found for all the metal ions were well correlated with the formation constants of iminodiacetate complexes in aqueous solutions. The actual adsorption of group 3 metal ions was significantly enhanced beyond that expected from this correlation because of the formation of (-L)(3)H(3)M. This is why the selectivity in the adsorption of trivalent metal ions differs from that in the complexation of iminodiacetate in aqueous solutions. The effects of anions and the number of iminodiacetic acid groups per unit weight of resins were also discussed.     

Multistimuli Sensing Adhesion Unit for the Self‐Positioning of Minimal Synthetic Cells

Cells have the ability to sense different environmental signals and position themselves accordingly in order to support their survival. Introducing analogous capabilities to the bottom‐up assembled minimal synthetic cells is an important step for their autonomy. Here, a minimal synthetic cell which combines a multistimuli sensitive adhesion unit with an energy conversion module is reported, such that it can adhere to places that have the right environmental parameters for ATP production. The multistimuli sensitive adhesion unit senses light, pH, oxidative stress, and the presence of metal ions and can regulate the adhesion of synthetic cells to substrates in response to these stimuli following a chemically coded logic. The adhesion unit is composed of the light and redox responsive protein interaction of iLID and Nano and the pH sensitive and metal ion mediated binding of protein His‐tags to Ni²⁺‐NTA complexes. Integration of the adhesion unit with a light to ATP conversion module into one synthetic cell allows it to adhere to places under blue light illumination, non‐oxidative conditions, at neutral pH and in the presence of metal ions, which are the right conditions to synthesize ATP. Thus, the multistimuli responsive adhesion unit allows synthetic cells to self‐position and execute their functions.     

Design of an i.v. formulation of an unstable prodrug candidate for prostate cancer treatment: solution chemistry of N-(glutaryl-hyp-ala-ser-cyclohexylglycyl-gln-ser-leu)-doxorubicin

The chemical degradation of N-(glutaryl-hyp-ala-ser-cyclohexylglycyl-gln-ser-leu)-doxorubicin (henceforth referred to as doxorubicin peptide conjugate 1) was studied in buffered aqueous solution. The pH-rate profile of degradation shows that the doxorubicin conjugate is most stable between pH 5 and 6. The dependence of log k_obsd on pH in acidic medium is characteristic of specific acid-catalysis of the sugar hemiaminal of 1 (as in the case of doxorubicin). Isolation of degradates and structural determination shows that the degradation at lower pH values yields the water-insoluble aglycone doxorubicinone, supporting the mechanism of acid-catalyzed loss of the amino sugar. At pH higher than 5, a more complicated degradation pattern is observed, including the loss of the amino sugar and the aromatization of the saturated ring to give 7,8-dehydro-9,10-desacetyldoxorubicinone as one of the major products. Around the pH of maximum stability in solution, the rate of degradation of 1 is significantly greater than that for doxorubicin, which rules out the formulation of a room temperature solution product with a sufficiently long shelflife for market use. Design of a stable lyophilized formulation for sterile reconstitution based on the physicochemical properties of 1 is described.     

Preparation and adsorption behavior of aminated electrospun polyacrylonitrile nanofiber mats for heavy metal ion removal

Polyacrylonitrile (PAN) nanofiber mats were prepared by electrospinning and they were further modified to contain amidino diethylenediamine chelating groups on their surface via heterogeneous reaction with diethylenetriamine (DETA). The obtained aminated PAN (APAN) nanofiber mats were evaluated for their chelating property with four types of metal ions, namely Cu(II), Ag(I), Fe(II), and Pb(II) ions. The amounts of the metal ions adsorbed onto the APAN nanofiber mats were influenced by the initial pH and the initial concentration of the metal ion solutions. Increasing the contact time also resulted in a monotonous increase in the adsorbed amounts of the metal ions, which finally reached equilibria at about 10 h for Cu(II) ions and about 5 h for Ag(I), Fe(II), and Pb(II) ions. The maximal adsorption capacities of the metal ions on the APAN nanofiber mats, as calculated from the Langmuir model, were 150.6, 155.5, 116.5, and 60.6 mg g(-1), respectively. Lastly, the spent APAN nanofiber mats could be facilely regenerated with a hydrochloric acid (HCl) aqueous solution.     

THE EFFECT OF TARTRATE, A WEAK COMPLEXING AGENT, ON THE REMOVAL OF HEAVY METALS BY SULFIDE AND HYDROXIDE PRECIPITATION

Industrial vastevaters generated in the electroplating and metal finishing industries typically contain toxic heavy metals. Depending on their origin, these wastewaters may also contain chelating agents, such as EDTA, NTA, citrate, tartrate, and gluconic acid. Although the major effect of complexation is an increase in the solubility of complexed metal ions, significant changes in the precipitation kinetics and particle size distribution may also contribute to the observed precipitation behavior.

This paper addresses the effect of a weak complexing agent, tartrate, on the removal of zinc and cadmium using both hydroxide and sulfide treatment. Results are presented on the removal of heavy metals from synthetic plating wastewaters. Poor zinc removals were observed in the presence of tartrate, particularly when larger filter pore sizes were employed. The results suggest that tartrate severely hinders both zinc hydroxide and zinc sulfide precipitation, resulting in the formation of very fine precipitates; this was confirmed when no zinc removal occurred even with a settling time of 30 min. For removal of cadmium, virtually no change in residual cadmium concentration was observed in the presence of tartrate (compared to the case of no complexing agents present) due to the formation of low-stability complexes.     

Determination of dissolved metal species by electrospray ionization mass spectrometry

The distribution of metal species in solution was determined using flow injection electrospray ionization mass spectrometry. Complexes formed by selected metal ions with added organic ligands in 50:50 water/acetonitrile and 50:50 water/methanol under acidic, neutral, and basic conditions were detected using electrospray ionization conditions optimized to best represent solution-phase interactions. Metal species containing acetate, nitrate, and solvent molecules predominated in acidic solution but became less abundant at higher pH. Interactions between metal ions and added organic ligands became more selective with increasing pH, showing the expected preference of hard and soft ligands for metal ions of the corresponding type. Species distributions also tended toward larger complexes as pH increased. Overall ion yield was greater for aqueous acetonitrile than for aqueous methanol solutions; however, reduction of copper(II) in aqueous acetonitrile resulted in the detection of copper(I) complexes for certain ligands. Experimental results for copper(II) and 8-hydroxyquinoline in 50:50 water/methanol showed good agreement with aqueous speciation predicted using the thermodynamic equilibrium model MINEQL. Detection of neutral complexes was achieved by protonation, deprotonation, or electrochemical oxidation during electrospray.     

The oxidative degradation of 2-mercaptobenzothiazole at the interface of beta-MnO2 and water

To investigate the oxidative degradation of organic pollutants at the interface of manganese oxides and water, beta-MnO2 was prepared and its crystal structure and the specific surface area were examined by X-ray diffraction (XRD) and Brunauer-Emmett-Teller (BET) methods, respectively. 2-Mercaptobenzothiazole (MBT) as a model chemical was used to study its oxidative degradation reaction in beta-MnO2 suspension. The experimental results showed that MBT was effectively degraded and mineralized into SO4(2-) and NO3- by beta-MnO2. In the meantime, it was found that beta-MnO2 could be reductively dissolved, and aqueous and adsorbed Mn2+ was generated. The kinetics of MBT degradation by beta-MnO2 is a function of initial MBT concentration, beta-MnO2 dosage and pH value. At pH 4.6, apparent reaction orders with respect to initial MBT concentration and beta-MnO2 dosage were determined to be 0.88 and 0.27, respectively. The initial reaction rate (rinit) is of pH dependence with a reaction order of -0.36. The thermodynamics of MBT degradation by beta-MnO2 was also investigated, and the apparent activation energy was calculated to be 5.62 kJ/mol. The inhibited effect of carboxylic acids (oxalic, citric, tartaric, and malic acids) or metal ions (Ni2+, Ca2+, Mn2+ and Cr3+) on the oxidative degradation of MBT by beta-MnO2 was also investigated. This investigation will give some new insights for understanding the interaction of organic pollutants with manganese oxides in natural soils and sediments.     

Decomposition of Anthralin in Alkaline Solutions

Abstract

Using conventional absorbance spectra and a first-derivative transformation technique anthralin was shown to undergo apparent first-order decomposition. The pH-log rate profile for the rate of disappearance of anthralin from aqueous solutions was determined at 25°C in the pH range of 7.74 to 10.02 at an ionic strength of 0.5 M. The profile indicated a maximum near the pK_a of anthralin. Measured values of the half life of anthralin decreased from 43.9 min at pH 7.74 to 14.8 min at pH 9.44 and then increased to 18.4 min at pH 10.02. No primary kinetic salt effect was observed. Since it was thought likely that trace amounts of metal ions could catalyze the degradation of anthralin, the effect of disodium ethylenediamine-tetraacetic acid addition was also investigated; this chelating agent did not influence the rate. Thermodynamic parameters were calculated from the temperature dependency of the decomposition.     

Removal of gallium (III) ions from acidic aqueous solution by supercritical carbon dioxide extraction in the green separation process

Supercritical carbon dioxide extraction, which is a feasible "green" alternative, was applied in this study as a sample pretreatment step for the removal of gallium (III) ions from acidic aqueous solution. The effect of various process parameters, including various chelating agents, extraction pressure and temperature, dimensionless CO(2) volume, the concentration of the chelating agent, and the pH of the solution, governing the efficiency and throughput of the procedure were systematically investigated. The performance of the various chelating agents from different studies indicated that the extraction efficiency of supercritical CO(2) was in the order: thiopyridine (PySH)>thenoyltrifluoroacetone (TTAH)>acetylacetone (AcAcH). The optimal extraction pressure and temperature for the supercritical CO(2) extraction of gallium (III) with chelating agent PySH were found to be 70 degrees C and 3000psi, respectively. The optimum concentration of the chelating agent was found to be 50ppm. A value of 7.5 was selected as the optimum dimensionless CO(2) volume. The optimum pH of the solution for supercritical CO(2) extraction should fall in the range of 2.0-3.0.     

微波辅助溶胶凝胶自燃烧一步合成六角铁酸钡纳米晶及其磁性能

以乙二胺四乙酸柠檬酸+乙二醇为复合络合剂, 冷冻干燥去除溶胶中水分, 提高凝胶中金属离子与氧化剂的分布均匀性, 并利用微波辅助溶胶凝胶自燃烧一步合成了六角铁酸钡纳米晶. 所得纳米晶近于球形, 尺寸在50~100nm, 其饱和磁化强度为338.5kA/m, 矫顽场仅为20.7kA/m. 分析表明, 富氧条件有利于避免自燃烧过程中由于有机物还原引起的铁元素分布不均匀, 从而有利于铁酸钡的相形成.