Effects of Temperature and Common Ions on Binding of Puerarin to BSA

The effects of temperature and common ions on binding of puerarin to bovine serum albumin (BSA) are investigated. The binding constants (K _a) between puerarin and BSA are 1.13×10⁴ L⋅mol⁻¹ (20 °C) and 1.54×10⁴ L⋅mol⁻¹ (30 °C), and the number of binding sites (n) is (0.95±0.02). However, at a higher temperature (40 °C) the stability of the puerarin–BSA system decreases, which results in a lower binding constant (1.58×10³ L⋅mol⁻¹) and number of binding sites (n=0.73) of the puerarin–BSA system. However, the presence of Cu²⁺ and Fe³⁺ ions increases the binding constants and the number of binding sites in the puerarin–BSA complex.     

157 nm Photodissociation of a Complete Set of Dipeptide Ions Containing C-Terminal Arginine

Twenty singly-charged dipeptide ions with C-terminal arginine were photodissociated with 157 nm light and their tandem mass spectra recorded. Many of the small product ions that were observed are standard peptide fragments that have been commonly seen in VUV photodissociation studies. However, the study of a library of dipeptides containing all 20 N-terminal amino acids enabled the recognition of trends associated with the occurrence of w-, v-, and immonium ions, the observation of competition between forming N- and C-terminal fragments in dipeptide RR, and the identification of some unusual fragment ions appearing at masses of 183, 187, 196, and 197 Da. A highly accurate internal calibration of the photodissociation TOF-TOF data enabled molecular formulae for these four product ions to be derived. Their proposed structures reflect the rather high-energy nature of this fragmentation phenomenon.      

Complexation Studies of Pyridyl Sulfonamide Ligands for Sensing Zinc and Copper Ions

Ligand protonation and stepwise dissociation constants, formation constants and speciation of four pyridyl sulfonamide ligands (Congreeve et al., New J. Chem. 27:98–106, 2003) were assessed, using potentiometric and UV/Visible spectrophotometric pH titrations (in 80% MeOH − 20% H₂O). The suitability of these ligands as Cu(II) and Zn(II) sensors for physiological applications was assessed. Two ligands L¹ and L⁴ were p-toluenesulfonamide derivatives while L² and L³ were triflurosulfonamide derivatives. Additionally L³ and L⁴ were appended with α-methyl groups. The most stable complex was formed by L¹ with Cu(II) owing to the fact that this complex was square planar (log ₁₀  K ₁=12.15±0.004 and log ₁₀  β ₂=15.42±0.006). The rest of the complexes invariably formed distorted tetrahedron geometry and complexation was weaker. Speciation diagrams show the effect of ligand to metal concentration, revealing that the L² and L³ ligands are the most suitable for forming ML₂ complexes at physiological pH.     

Complexation Studies of N,N′-ethylenedi-L-cysteine with Some Metal Ions

As part of a search for environmentally friendly metal chelating ligands, the stability constants of N, N′-ethylenedi-L-cysteine (EC) complexes with Ca(II), Cu(II), Mg(II) and Mn(II) were determined by potentiometry with a glass electrode in aqueous solutions containing 0.1 mol⋅L⁻¹ KCl at 25 °C. Final models are proposed. For the Ca(II)–EC system, the overall stability constants are log ₁₀ β _CaHL=14.53±0.03, log ₁₀ β _CaL=4.79±0.01 and log ₁₀ β _CaL2=8.38±0.04. For the M(II)–EC systems, where M=Cu(II) or Mg(II), the overall stability constants are log₁₀ β _CuHL=31.19±0.02 and log ₁₀ β _CuL=27.02±0.06 for Cu(II), and are log ₁₀ β _MgHL=14.84±0.02 and log ₁₀ β _MgL=6.164±0.008 for Mg(II). For the Mn(II)–EC system, the overall stability constant is log ₁₀ β _MnL=10.12±0.01. Metal–chelate speciations simulations showed that EC is an efficient chelating agent for Cd(II), Co(II), Cu(II), Ni(II), Pb(II) and Zn(II) for pH≥7.     

Stability and Coordination Mode of Complexes of Polyphosphates and Polymetaphosphates with Copper(II) Ions in Aqueous Solution—Potentiometric,Spectral and Theoretical Studies

Complexes of copper(II) with a number of polyphosphate and polymetaphosphate anions have been studied in aqueous solutions by potentiometric, spectroscopic and theoretical methods. Stability constants of the complexes have been determined as well as their coordination modes. Results of the equilibrium studies provided evidence for the formation of ML, MHL and ML(OH) _x type complexes with the ligands studied. The length of the polyphosphate chain was found to affect the oxygen atom charge that is reflected in the stability constants of the ML type complexes. Moreover, the stability of the complex is also influenced by the spatial arrangement of the phosphate groups in phosphates and metaphosphates. The spectral parameters observed for certain complexes have permitted us to deduce the inner coordination sphere of the studied complexes.     

Adsorption of Ions on Zirconium Oxide Surfaces from Aqueous Solutions at High Temperatures

Surface titrations were carried out on suspensions of monoclinic ZrO₂ from 25 to 290 °C slightly above saturation vapor pressure at ionic strengths of 0.03, 0.1 and 1.0 mol⋅kg⁻¹(NaCl). A typical increase in surface charge was observed with increasing temperature. There was no correlation between the radius of the cations, Li⁺, Na⁺, K⁺ and (CH₃)₄N⁺, and the magnitude of their association with the surface. The combined results were treated with a 1-pK_a MUSIC model, which yielded association constants for the cations (and chloride ion at low pH) at each temperature. The pH of zero-point-charge, pH_zpc, decreased with increasing temperature as found for other metal oxides, reaching an apparent minimum value of 4.1 by 250 °C. Batch experiments were performed to monitor the concentration of LiOH in solutions containing suspended ZrO₂ particles from 200 to 360 °C. At 350 and 360 °C, Li⁺ and OH⁻ ions were almost totally adsorbed when the pressure was lowered to near saturation vapor pressure. This reversible trend has implications not only to pressure-water reactor, PWR, operations, but is also of general scientific and other applied interest. Additional experiments probed the feasibility that boric acid/borate ions adsorb reversibly onto ZrO₂ surfaces at near-neutral pH conditions as indicated in earlier publications. Electronic Supplementary Material  The online version of this article () contains supplementary material, which is available to authorized users.     

Redox Isomerism of α-Ferrocenylcarbenium Ions

The formation of α-ferrocenylcarbenium ions FcC⁺H₂ (λ_max 600 nm) and FcC⁺HCH₃ (λ_max 730 nm) and their redox isomerism at the protonation of ferrocenylmethanol and vinylferrocene was proved using the method of electronic spectroscopy. The effect on the process of the solvent and acid nature as well as of hydrogen peroxide additives is discussed.     

Volumetric Properties of Aqueous Solutions of L-Glutamic Acid and Magnesium-L-Glutamate

Densities of aqueous solutions of L-glutamic acid and magnesium-L-glutamate were determined from T=288.15 to 333.15 K at 5 K temperature intervals. The measured densities were used to evaluate the apparent molar volumes, V _2,φ (m,T), the cubic expansion coefficients, α(m,T), and the changes of isobaric heat capacities with respect to pressure, (∂ C _p /∂ p) _T,m . They were qualitatively correlated with changes in the structure of water that occur when L-glutamic acid or magnesium-L-glutamate are present.     

In Vitro Study of the Binding of Taxifolin to Bovine Serum Albumin and the Influence of Common Ions on the Binding

The interaction between taxifolin and bovine serum albumin (BSA), and the effects of some common ions on their interaction, were investigated by fluorescence and UV-visible absorption spectroscopy. The results indicate that taxifolin has a strong ability to quench the intrinsic fluorescence of BSA through a static quenching process. According to values of the thermodynamic parameters, the hydrophobic force plays a major role in the interaction. Based on Főster’s non-radiation theory, the energy transfer distances between BSA and taxifolin in the absence and presence of some common ions were obtained. The experimental results indicate that the transfer distances are almost unaffected by these ions. The conformation of BSA undergoes significant change from the formation of a taxifolin–BSA complex, which was studied by synchronous and three-dimensional fluorescence spectroscopy.     

Measurement of Magnesium Stability Constants of Biologically Relevant Ligands by Simultaneous Use of pH and Ion-Selective Electrodes

Simultaneous measurements with magnesium ion-selective and pH glass electrodes have been used for determination of the stability constants of magnesium ions with various biologically relevant ligands by alkalimetric titration under physiological conditions (37^○C, I=0.15 mol⋅dm⁻³). New systems were investigated: magnesium with pyroglutamate, pyridoxine and HEPES, along with citrate, lactate, glycinate, aspartate and glutamate. For comparison, calcium stability constants with the same ligands were determined similarly, using calcium ion-selective and pH glass electrodes. Ligand protonation constants, necessary for the calculation of the metal complex formation constants, were also determined.     

A Study of Metal Ions Packing Hydrated Layer of Inclusion Crystals

The inclusion crystal formed by the hexamethylenamine with p-nitrophenol has a layer type structure,and is divided or-ganic layer and inorganic layer,the latter has a width of 1.0136nm.Metal ions can enter hydrated layer of the crystal,the con-tents of the cations and water in the crystal are determined.The XRD analysis of the layer type structure of the crystal is also giv-en.     

Promoter Effects of Rare Earth Ions on Electrocatalytic Oxidation of Methanol

The promoter effects of rare earth ions on the electrocatalytic oxidation of methanol at the Pt electrode were studied using the cyclinc voltammetry and stable polarization techniques. It was found or the first time that Eu、Ho、Dy ions could accelerate the electrocatalytic oxidation of methanol at the Pt electrode,while Lu、Pr、Yb、Sm ions showed inhibitor effects.     

Determination of Activation Energy for the Diffusion of Fe<Superscript>3+</Superscript> Ions in Agar Gel Medium Containing Various Transition Metal Sulfates

The study of the diffusion of ferric ions in agar gel containing transition metal sulfates was carried out. The effect of gel concentration, electrolyte concentration and temperature on the diffusion of Fe³⁺ ions in various transition metal sulfates was studied with a view to verify Wang’s model of diffusion and the applicability of transition state theory to diffusion in a gel medium. The diffusion coefficients were measured using the zone diffusion technique. For a given concentration of electrolyte the activation energy (E) is found to decrease with an increase in the charge density of the cation of the supporting electrolyte and for a given system it is found to decrease with increasing electrolyte concentration in agreement with Wang’s model. This observation is explained on the basis of the distortion in the water structure caused by ions and agar molecules. At a given electrolyte concentration the magnitude of the Arrhenius parameters, E and D _o, is found to decrease with increasing gel concentration in agreement with the transition state theory of diffusion.     

Investigation of the Structures of the Product Ions Produced via self-CI of Acetone

TheacetoneselfCImassspectrumAcetoneselfCImassspectrumisgiveninTable1.Table1.MajorproductionsandtheirrelativeabundanceofacetoneselfCIMSTheformationofionatmlZ73AnotherproductionintheselfCIMSofacetoneistheionatm/z73.InselfCIMSofacetone-d6,thecounterpartistheionatInjz82.InselfCIMSofthemixtureofacetoneandacetone-d6inaratioofl:l,thecorrespondingionsaretheionsatInlz73,76,79and82.TheirCIDreactionresultsarelistedinTable2.Table2.TheCIDMSoftheionatIn/z73andanalogsOnthebasisofthedatainTab…     

Loss of 45 Da from a<Subscript>2</Subscript> Ions and Preferential Loss of 48 Da from a<Subscript>2</Subscript> Ions Containing Methionine in Peptide Ion Tandem Mass Spectra

While analyzing tandem mass spectra of tryptic tripeptides, intense unassigned peaks were observed, corresponding to neutral loss of 45 Da from a₂ ions. This process was confirmed by MS³ experiments. Based on exact mass analysis, the loss was ascribed to (NH₃ + CO) or formamide. The proposed mechanism involves a cyclic form of the a₂ ions. The structure of the a₂ − 45 ions was confirmed by their fragmentation in MS³ experiments. Loss of (NH₃ + CO) from the a₂ ions occurs in competition with other paths, such as the loss of H₂O or the formation of immonium ions. However, if the a₂ ion contains methionine, a neutral loss of 48 Da (ascribed to CH₃SH) predominates, and is followed by the loss of (NH₃ + CO). These processes were confirmed by MS³ experiments. The intensity of the a₂ − 48 peak formed from XaaMet has a maximum value of 42% (of the total intensity of all ions) for Xaa=Gly, varies between 15% and 40% for most other Xaa residues, is lower for residues that can undergo loss of water or ammonia, and is very low for Lys or Arg. When the order of the residues is reversed to MetXaa, the loss of 48 Da is much smaller. This effect can be used to determine the sequence of b₂ ions containing Met in proteomic studies. Considerable loss of CH₃SH is observed from doubly protonated tryptic tripeptides with N-terminal Met, but the loss is much less when they are singly protonated or when Met is in the center position.     

Volumetric Study of Aqueous Solutions of Polyethylene Glycol as a Function of the Polymer Molar Mass in the Temperature Range 283.15 to 313.15 K and 0.1 MPa

Density measurements were made for binary aqueous solutions of polyethylene glycol at seven temperatures: 283.15, 288.15, 293.15, 298.15, 303.15, 308.15, and 313.15 K. Polyethylene glycol samples with nominal average molar masses of 3000 g⋅mol⁻¹ (PEG 3000), 6000 g⋅mol⁻¹ (PEG 6000), 10000 g⋅mol⁻¹ (PEG 10000) and 20000 g⋅mol⁻¹ (PEG 20000) were used. These results were used to determine the specific volumes of solutions with solute-to-solvent mass ratios (mass of the solute/mass of the solvent) in the range 0.0546 to 1.4932 for PEG 3000, from 0.0553 to 1.4986 for PEG 6000, from 0.0552 to 1.2241 for PEG 10000, and from 0.0530 to 1.2264 for PEG 20000. The differences between the specific volume of a solution and the specific volume of the pure solvent, at a given temperature, were represented by a virial-type equation in terms of solute concentration. The first-order coefficient of the expansion is the partial specific volume of the solute at infinite dilution. The higher-order coefficients are related to the contribution of pairs, triplets, and higher-order solute aggregates, according to the Constant-Pressure Solution Theory. The functional dependence of the virial coefficients upon temperature is discussed in terms of solute-solute and solute-solvent interactions. The effect of the PEG molar mass on the partial specific volume of solute at infinite dilution, as well as the contributions of pairs of solute molecules to the solution volume, are also investigated. The apparent specific volume, apparent specific expansibility, apparent specific expansibility at infinite dilution and virial coefficients of the apparent specific expansibility are also presented.     

Temperature Dependence of Physical Properties of Imidazolium Based Ionic Liquids: Internal Pressure and Molar Refraction

Density, speed of sound and refractive index of the imidazolium-based ionic liquids (ILs), 1-methyl-3-octylimidazolium chloride [C₈mim][Cl], 1-butyl-3-methylimidazolium methyl sulfate [C₄mim][C₁OSO₃], and 1-butyl-3-methylimidazolium octyl sulfate [C₄mim][C₈OSO₃], have been measured in the temperature range from 283.15 to 343.15 K. Experimental density and speed of sound have been used to calculate the internal pressure p _i of the ILs. The p _i values were found to be higher than those of water and molecular organic liquids, but lower than those of classical molten salts. We also calculated molar refraction R _M from the measured refractive index n _D in the temperature range from 288.15 to 343.15 K. Refractive indices of ILs were also higher than those of normal organic liquids, but comparable to long-chain hydrocarbon organic solvents. The structure-property correlation of the ILs has been discussed and the results have been compared to our earlier studies (Kumar in J. Solution Chem. 37:203–214, 2008).     

Transformation of Structure and Properties of Vesicles Induced by Transition Metal Ions

This paper proved that octodecyl propylenediamine could form vesicles in pure water and aqueous solution of CuCl2 or Cu（NO3）2. The structure and morphology of vesicles were different when the copper （Ⅱ） salt was added to the solution. The results showed that both the counterions and the ligands had strong influence on the configuration of coordinated structures and packing model in bilayer membrane of vesicles.     

Synthesis Characterization and Viscosity Studies of Homopolymer of Methyl Methacrylate and Copolymer of Methyl Methacrylate and Styrene

A homopolymer of methyl methacrylate (MMA) and its copolymer with styrene at different compositions were synthesized and characterized. Viscosity measurements of the synthesized homopolymer and the copolymers in toluene solutions were performed at 313 K. Different equations were used to calculate the intrinsic viscosity, viscometric constants values, and molecular weight of the synthesized polymers. The values of intrinsic viscosity and viscosity average molecular weight obtained by the two methods (single point determination and graphical extrapolation) were compared in order to verify the validity of the single point determination for the polymers. Viscometric properties derived included the specific viscosity (it determines the contribution of the solute to the viscosity of the solution), the reduced viscosity (that provides a measure of the polymer capacity for increasing the solution viscosity), and the intrinsic viscosity.