Studies on yellow and colourless molybdophosphate complexes in the aqueous solution by laser raman spectroscopy

Yellow and colourless complexes of molybdophosphate were investigated by the use of laser Raman spectroscopy. Two kinds of yellow molybdophosphates were identified in the weakly acidic solutions: 12-molybdophosphoric and 11-molybdophosphoric acid which are in equilibrium in solution at pH 1-2. When excess phosphate is present, the colourless molybdophosphate is formed. This complex exists in the solutions of pH 4-1 under the condition of excess phosphate ([P]/[Mo] > 2). This complex was confirmed to be P₂Mo₅O^6?₂₃ and is so stable that the yellow molybdophosphate is converted into the colourless by excess phosphate.     

Study on the fluoride adsorption of various apatite materials in aqueous solution

The aim of this study was to evaluate the defluoridation efficiencies of various sorbents in aqueous solution. These sorbents include synthetic nano-hydroxyapatite (n-HAp), biogenic apatite (bone meal), treated biogenic apatite (bone meal prepared by H₂O₂ oxidation) and geogenic apatite (rock phosphate), which were characterized by XRD, FTIR, TEM and SEM. It has been observed that the defluoridation capacities follow the order: n-HAp > BH₂O₂ > B > rock phosphate. The controlling factors, sorbent dose, initial fluoride concentration, pH, contact time and temperature were investigated. The defluoridation capacities increased with the increase in the initial fluoride concentration and contact time, decreased with the increase in the sorbent dose. The optimum pH range for removal of fluoride on various apatite sorbents was considered to be 5.0-6.0. The fluoride adsorption can be explained by Langmuir, Freundlich isotherms, and the adsorption kinetic data follow the pseudo-second-order model. Thermodynamic parameters such as ΔH⁰, ΔS⁰ and ΔG⁰ indicated that the adsorption on various apatite sorbents was spontaneous and endothermic. These results showed that bone meal is a promising material for fluoride adsorption.     

Effect of solvent-water mixtures on the prototropic equilibria of fluorescein and on the spectral properties of the monoanion

A spectral resolution procedure was used to resolve the absorption, excitation and emission spectra of the fluorescein monoanion in a number of solvent-water mixtures. This permitted an analysis of the effect of the solvent environment on the spectral properties of the monoanion and on the lactone/monoanion/dianion transitions of fluorescein. The monoanion excitation and emission spectra show relatively small changes with changing environment, a behavior that is related to the hydrogen-bonding environment of the solvent-water mixtures. There is also a general increase in the quantum yield of the monoanion from 0.36 in water to values up to 0.49 in the solvent-water mixtures. The presence of solvent also results in a general increase in the lactone content and in the monoanion:dianion and lactone:monoanion ratios. General polarity effects alone cannot account for the observed effects on the prototropic transitions indicating that specific solute-solvent effects involving hydrogen bonding perturb the prototropic equilibria of fluorescein.     

Studies on fluorescein-II The solubility and acid dissociation constants of fluorescein in water solution

The solubility of yellow fluorescein and of red fluorescein as a function of pH has been measured in water at ionic strength 0.10. The pH of minimum solubility is the same for both, 3.28. The intrinsic solubility, defined as the solubility of the undissociated species, H(2)Fl, and assumed to be constant and independent of pH, was calculated from the observed solubilities on the low-pH side of the minimum: S(i, yellow) = 3.80 x 10(-4)M: S(i, red) = 1.45 x 10(-4)M. The first dissociation constants were evaluated from the intrinsic solubilities and the observed solubilities on the low-pH side: both fluoresceins yielded the same value, pK(H3Fl) = 2.13. In using the observed solubilities on the high-pH side of the minimum to evaluate the intrinsic solubility and the second dissociation constant it was necessary to modify the existing theoretical approach by taking into account the presence of the fully dissociated anion. Appropriate mathematical treatments were devised to handle the more complex equations. Both fluoresceins yielded the same value for the second dissociation constant, pK(H2Fl) = 4.44. Both fluoresceins give the same yellow colour in saturated solution and the results just reported for the pH of minimum solubility and for the dissociation constants also indicate that for each of the three prototropic forms of fluorescein present in solution, H(3)Fl(+), H(2)Fl, and HFl(-), only one structure exists.     

Investigation of the effects of various parameters on the synthesis of oligopeptides in aqueous solution

Oligomerization efficiency of amino acids in aqueous solution has been compared under different conditions (temperature, activating agent, etc.) using 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) and 1,1^′-carbonyldiimidazole (CDI) as coupling agents. Glycine (H₂N-CH₂-COOH) and α-alanine (H₂N-CH(CH₃)-COOH) were chosen as α-amino acids and β-alanine (H₂N-CH₂-CH₂-COOH) as the β-amino acid. The coupling reaction between EDC and glycine was shown to occur but does not go to completion either at ambient temperature or at 70 °C. The presence of a carboxylic activating agent such as N-hydroxysuccinimide improves the EDC-mediated coupling reaction, and the amino acid structure (α- or β-) was shown to have an influence on the oligomerization efficiency, with β-alanine polymerisation being more efficient. These findings are explained by reference to the reaction mechanism.     

Direct nitric oxide detection in aqueous solution by copper(II) fluorescein complexes

A series of FL(n) (n = 1-5) ligands, where FL(n) is a fluorescein modified with a functionalized 8-aminoquinoline group as a copper-binding moiety, were synthesized, and the chemical and photophysical properties of the free ligands and their copper complexes were investigated. UV-visible spectroscopy revealed a 1:1 binding stoichiometry for the Cu(II) complexes of FL(1), FL(3), and FL(5) in pH 7.0 buffered aqueous solutions. The reactions of FL(2) or FL(4) with CuCl(2), however, appear to produce a mixture of 1:1 and 1:2 complexes, as suggested by Job's plots. These binding modes were modeled by the synthesis and X-ray crystal structure determination of Cu(II) complexes of 2-[(quinolin-8-ylamino)methyl]phenol (modL), employed as a surrogate of the FL(n) ligand family. Two kinds of crystals, [Cu(modL)(2)](BF(4))(2) and [Cu(2)(modL')(2)(CH(3)OH)](BF(4))(2) (modL' = 2-[(quinolin-8-ylamino)methyl]phenolate), were obtained. The structures suggest that one oxygen and two nitrogen atoms of the FL(n) ligands most likely bind to Cu(II). Introduction of nitric oxide (NO) to pH 7.0 buffered aqueous solutions of Cu(FL(n)) (1 microM CuCl(2) and 1 microM FL(n)) at 37 degrees C induces an increase in fluorescence. The fluorescence response of Cu(FL(n)) to NO is direct and specific, which is a significant improvement over commercially available small molecule-based probes that are capable of detecting NO only indirectly. The NO-triggered fluorescence increase of Cu(FL(5)) occurs by reduction of Cu(II) to Cu(I) with concomitant dissociation of the N-nitrosated fluorophore ligand from copper. Spectroscopic and product analyses of the reaction of the FL(5) copper complex with NO indicated that the N-nitrosated fluorescein ligand (FL(5)-NO) is the species responsible for fluorescence turn-on. Density functional theory (DFT) calculations of FL(5) versus FL(5)-NO reveal how N-nitrosation of the fluorophore ligand brings about the fluorescence increase. The copper-based probes described in the present work form the basis for real-time detection of nitric oxide production in living cells.     

Aggregation behavior of hexadecyltrimethylammonium surfactants with various counterions in aqueous solution

Both thermodynamic and microenvironmental properties of the micelles for a series of cationic surfactants hexadecyltrimethylammonium (C16TAX) with different counterions, F-, Cl-, Br-, NO3-, and (1/2)SO4(2-), have been studied. Critical micelle concentration (CMC), degree of micelle ionization (alpha), and enthalpy of micellization (DeltaH(mic)) have been obtained by conductivity measurements and isothermal titration microcalorimetry. Both the CMC and the alpha increase in the order SO4(2-) < NO3- < Br- < Cl- < F-, consistent with a decrease in binding of counterion, except for the divalent anion sulfate. DeltaH(mic) becomes less negative through the sequence NO3- < Br- < Cl- < F- < SO4(2-), and even becomes positive for the divalent sulfate. The special behavior of sulfate is associated with both its divalency and its degree of dehydration. Gibbs free energies of micellization (DeltaG(mic)) and entropies of micellization (DeltaS(mic)) have been calculated from the values of DeltaH(mic), CMC, and alpha and can be rationalized in terms of the Hofmeister series. The variations in DeltaH(mic) and DeltaS(mic) have been compared with those for the corresponding series of gemini surfactants. Electron spin resonance has been used to assess the micropolarity and the microviscosity of the micelles. The results show that the microenvironment of the spin probe in the C16TAX surfactant micelles depends strongly on the binding of the counterion.     

Effect of various halide salts on the incompatibility of cyanocobalamin and ascorbic acid in aqueous solution

Combination of cyanocobalamin (VB12) and ascorbic acid (VC) has been widely seen in pharmaceutical products and dietary supplements. However, VB12 has been reported that its behavior in stability in aqueous solution is quite different when VC is mixed. In the present study, we examined the stabilities of these vitamins in acetate buffer (pH 4.8) using high performance liquid chromatography. Degradation of VB12 was not observed in the absence of VC in the buffer. However, when VC was mixed in the VB12 solution, VB12 concentrations decreased in accordance with VC degradation. VB12 and VC degradations were inhibited by adding sodium halides to acetate buffer at pH 4.8. These stabilization effects were also observed in the range from pH 3.5 to 5.3 and by adding potassium, magnesium, and calcium halides. Furthermore, our data demonstrated that increases in the halide anion concentrations and atomic number (Cl-相似文献   

Interactions between cyclic phosphate anions and various cations in aqueous solution

Interactions of tetrameta-, hexameta- and octameta-phosphate ions with proton, alkali metal ions and hexamminecobalt(III) ion were studied by the conductivity and potentiometric method. It was shown that the logarithms of thermodynamic stability constants of 1 : 1 proton associated molecules with these cyclic phosphates increase linearly with the anion charges contrary to those with the linear phosphates. The anomalous order of the stability constants obtained for alkali metal ion-pairs with a cyclic phosphate suggests the possibility of partial dehydration of the alkali metal ions with smaller atomic weights in the ion-pair formation. By the use of ion-selective electrodes, it was shown that in a solution containing an excess of sodium, potassium or rubidium ions compared with cyclic phosphate ions, more than one cation is associated with a cyclic phosphate ion. The apparent association constants of these highly associated species were determined. Interactions of cyclic phosphate ions with hexamminecobalt(III) ion, which was selected as an example of tervalent cations, are discussed in comparison with those for uni- and bi-valent cation complexes.     

Electrogenerated chemiluminescence of fluorescein in aqueous alkaline solutions

Fluorescein is shown to emit light when electrolyzed either anodically or cathodically using potential pulses, in aqueous alkaline solutions at a platinum electrode.     

Fluorescent sensing of pyrophosphate and ATP in 100% aqueous solution using a fluorescein derivative and Mn

A new fluorescein derivative has been synthesized for the detection of pyrophosphate (PPi) and ATP in 100% aqueous solution. Chemosensor 1 in the presence of Mn²⁺ (2.5 equiv) displayed selective fluorescent enhancements with PPi and ATP at pH 7.4. among the anions examined. The association constant of 1 in the presence of Mn²⁺ with PPi and ATP was calculated as 4.2 × 10⁴ and 3.5 × 10⁴ M⁻¹.     

杂原子对Y沸石液固相类质同晶取代规律探讨

用NH~4BF~4,(NH~4)~3ZrF~7,(NH~4)~2Tif~6,(NH~4)~3FeF~6和CrF~3,3NH~4F等溶液为取代剂,对Y沸石实行液固相类质同晶取代,除了B以外, 其它金属元素均能代入沸石骨架,它们的取代程度为Fe>Ti>Cr≈Zr.采用XRD,IR和DTA 等手段对取代产物进行表征,证实杂原子已成为骨架元素.由液固相类质同晶取代机理出发, 对影响杂原子取代程度的主要因素进行了探讨,提出由杂原子的离子半径.含氟配合物累积稳定常数. 阳离子水解平衡常数和水解产物聚合平衡常数可以预测各种杂原子的取代效果.     

Studies on microstructure and aqueous solution properties of block copolymer of acrylamide-styrene

Three series of block copolymers of acrylamide (AM) and styrene (St) as hydrophobic comonomer with varied microstructures were prepared in microemulsion medium by changing feed ratio of monomers, ratio of St to surfactant, and amount of initiator, respectively. The effects of microstructure factors of the amphiphilic block copolymers PAM-b-PSt on their aqueous solution properties were investigated by fluorescence probe technique and surface tension measurement in detail. The experimental results show that the aqueous solution properties of PAM-b-PSt are strongly dependent on their microstructure factors, such as the length and content of PSt hydrophobic blocks in the copolymers and their molecular weight. It was found that the main microstructure factors which effect the hydrophobic association behavior of the copolymer PAM-b-PSt are the length and content of PSt hydrophobic blocks in the copolymer, whereas the hydrophobic association behavior of the copolymer is not affected nearly so much by molecular weight in more dilute regions. At the same time, it was also found that the main microstructure factors which affect the surface activity of the copolymer are the content of PSt hydrophobic blocks in the copolymer and molecular weight, whereas the length of PSt blocks in copolymer does not affect surface activity of the copolymer nearly so much under fixed content of PSt hydrophobic blocks and molecular weight in the copolymer.     

The rate of loss of mercury from aqueous solution when stored in various containers

Solutions of natural water and distilled water were spiked with mercury(II) (25 p.p.b.) and stored in polyethylene, polyvinyl chloride, and soft glass containers. Losses of mercury at different pH values were monitored by flameless atomic absorption for a total of 17 days. Severe losses of mercury were observed at pH 2 and 7. Mercury loss from solution followed first-order kinetics; the half-lives of mercury loss under various conditions were calculated. Acidification of the solutions to pH 0.5 with nitric acid curtailed mercury loss substantially. Possible ways of reducing the loss of mercury from environmental water samples are discussed.     

氮氧自由基研究XVII:水溶液中哌啶氮氧自由基的电化学行为和自衰变动力学研究

循环伏安法研究表明,2,2,6,6-四甲基-4-羟基哌啶-1-氧自由基和2,2,6,6-四甲基-4-氧哌啶-1-氧自由基,在水溶液中的单电子氧化电极反应的可逆性随介质酸性,扫描速度和自由基浓度增加而增加,表明电极氧化产物可进一步发生化学反应.     

X-ray irradiation-assisted low-temperature synthesis of yellow lead(II) oxide (massicot) in aqueous solution

Processes occurring in the lead(II)-hydroxide anion system in aqueous solutions at pH > 12 and an ambient temperature (20–25°C) irradiated simultaneously with X-rays at a wavelength of 0.01–1.0 nm were considered. It was shown that the yellow polymorph of the oxide PbO (massicot) precipitated from the solution after a relatively short period of time under the given specific conditions, a development that can be of use for the manufacture of this compound.