A voltammetric study of the binding of copper(II) to peptide fragments of prion

Binding of copper to three peptide fragments of prion (Cu²⁺ binding sites: 60–91, 92–96 and 180–193 amino acid residues) was investigated by anodic stripping voltammetry to determine the stoichiometries of Cu²⁺-prion peptide interactions. The method relies on the synthesis of N-terminally acetylated/C-terminally amidated peptide fragments of prion by solid-phase synthesis and direct monitoring of the oxidation current of copper in the absence and presence of each prion fragment. Titration curves of Cu²⁺ with Ac-PHGGGWGQ-NH₂, Ac-GGGTH-NH₂ and Ac-VNITKQHTVTTTT-NH₂ were obtained in concentrations ranging from 8.52 × 10^?7 to 5.08 × 10^?6, 3.95 × 10^?7 to 1.94 × 10^?6 and 7.82 × 10^?8 to 4.51 × 10^?7 M, respectively. The acquired data were used to calculate the stoichiometries (one peptide per Cu²⁺ ion for all the three studied systems) and apparent dissociation constants (K_d = 4.37 × 10^?8–3.50 × 10^?10 M) for the three complexes.     

Molecular interaction of organic dyes in bulk and confined media

Molecular interactions of five thiazine dyes with increasing alkyl substitution have been studied in aqueous and microemulsion media at 303 K within a concentration range of (1.35–7.00) × 10^?4 M. The dimerization constant (K_d) values for the five dyes are ranged between 1.761 and 6.258 × 10³ l mol^?1 in bulk water media, where as in microemulsion media, K_d's are ranged between 1.760 and 4.110 × 10³ l mol^?1. Thionine (with no methyl substitution) and azure A (with two methyl substitution) displayed slightly larger K_d values in microemulsion water pools compared to bulk water while other dyes recorded significant drop in K_d values. The influence of microemulsion media on the molecular interaction of dyes has been explained in terms of electrostatic and hydrophobic factors. The monomer and the dimer spectra are explained in terms of molecular exciton model and the optical absorption parameters of both the species are reported in bulk and confined media.     

Flow-injection chemiluminescence determination of dihydralazine sulfate in serum using luminol and diperiodatocuprate (III) system

A novel flow-injection chemiluminescence (CL) method for the determination of dihydralazine sulfate (DHZS) is described. The method is based on the reaction of luminol and diperiodatocuprate (K₂[Cu(H₂IO₆)(OH)₂], DPC) in alkaline medium to emit CL, which is greatly enhanced by DHZS. The possible CL mechanism was first proposed based on the kinetic characteristic, CL spectrum and UV spectra. The optimum condition for the CL reaction was in detail studied using flow-injection system. The experiments indicated that under optimum condition, the CL intensity was linearly related to the concentration of DHZS in the range of 7.0 × 10^?9 to 8.6 × 10^?7 g mL^?1 with a detection limit (3σ) of 2.1 × 10^?9 g mL^?1. The proposed method had good reproducibility with the relative standard deviation 3.1% (n = 7) for 5.2 × 10^?8 g mL^?1 of DHZS. This method has the advantages of simple operation, fast response and high sensitivity. The special advantage of the system is that very low concentration of luminol can react with DPC catalyzed by DHZS to get excellent experiment results. And CL cannot be observed nearly when luminol with same concentration reacts with other oxidants, so luminol–DPC system has higher selectivity than other luminol CL systems. The method has been successfully applied to determine DHZS in serum.     

Spectrophotometric determination of diphenhydramine hydrochloride in pharmaceutical preparations and biological fluids via ion-pair formation

A simple, sensitive and accurate spectrophotometric method has been described for the assay of diphenhydramine hydrochloride (DPH) in raw material and in biological samples. The method is based on extraction of DPH into dichloromethane as ion-pair complexes with patent blue (PB), eriochrome black T (EBT), methyl orange (MO) and bromocresol purple (BCP) in acidic medium. The coloured species exhibited absorption maxima at 632, 514, 428 and 414 nm for PB, EBT, MO and BCP, with molar absorptivity values of 1.32 × 10⁵, 2.36 × 10⁴, 3.68 × 10⁴ and 3.07 × 10⁴ l mol^?1 cm^?1, respectively. The reaction conditions were optimized to obtain the maximum colour intensity. Beer’s law was obeyed with a good correlation coefficient (0.9982–0.9993) in the concentration ranges 0.5–3, 2.0–16, 2.0–10 and 1.0–10 μg ml^?1 for PB, EBT, MO and BCP methods, respectively. The composition ratio of the ion-association complexes was found to be 1:1 in all cases as established by Job’s method. The conditional stability constant (K_f) and the free energy changes (ΔG°) were determined for all complexes formed. The proposed method was successfully applied for the determination of DPH in tablets and human urine with good accuracy and precision. Statistical comparison of the results with those obtained by the official method showed good agreement and indicated no significant difference in accuracy and precision.     

Photophysical and photochemical studies of thifensulfuron-methyl herbicide in aqueous solution

The photophysical and photochemical studies of a sulfonylurea herbicide, thifensulfuron-methyl (THM), have been investigated in a buffered aqueous solution. In the first part, the influence of pH on the spectroscopic properties was studied. This allowed the determination of the ground and excited state acidity constants, pK_a = 4 and 4.4, respectively, thus exhibiting the potential existence of a photoinduced protonation in the singlet state. In the second part, the photolysis kinetics was studied at different pH and varying oxygen concentrations, using an HPK 125 W lamp and followed up by the identification of photoproducts formed under continuous photo-irradiation. The kinetics results suggest that the photolysis process is faster in acidic (k = 3 × 10^?4 s^?1) than in basic medium (k = 9.8 × 10^?5 s^?1). The photolysis products were identified by high performance liquid chromatography HPLC-DAD, HPLC–MS and HPLC–MS–MS. In order to obtain a better understanding of the photodegradation mechanism, a laser flash photolysis study was performed. By comparing the quenching rate constant (k_q = 9.64 × 10⁸ mol^?1 l s^?1) obtained from triplet state quenching by molecular oxygen and from the Stern–Volmer relation (k_q = 0.41 × 10⁸ mol^?1 l s^?1), the role of the singlet state in the photodegradation process was demonstrated. The photoproducts originating from both singlet and triplet excited states have been identified and hypothetical photodegradation pathways of the thifensulfuron-methyl in aqueous solution are proposed.     

Highly selective thiocyanate electrode based on bis-bebzoin-semitriethylenetetraamine binuclear copper(II) complex as neutral carrier

A novel selective thiocyanate PVC membrane electrode based on bis-bebzoin-semitriethylenetetraamine binuclear copper(II) [Cu(II)₂–BBSTA] as neutral carrier is reported, which displays an anti-Hofmeister selectivity sequence in following order: SCN⁻ > ClO₄⁻ > I⁻ >Sal⁻ >SO₃²⁻ >NO₃⁻ > H₂PO₄⁻ > Cl⁻ >NO₂⁻ > SO₄²⁻. The electrode exhibits Nernstian potential linear range to thiocyanate from 1.0 × 10⁻¹ to 9.0 × 10⁻⁷ mol/l with a detection limit 7.0 × 10⁻⁷ mol/l and a slope of −57.0 mV/decade in pH 5.0 of phosphorate buffer solution at 25 °C. The response mechanism is discussed in view of the AC impedance technique and the UV spectroscopy technique. From comparison of potentiometric response characteristics between the binuclear metallic complex copper(II) [Cu(II)₂–BBSTA] and mononuclear copper(II) metallic complex [Cu(II)–BBSDA], an enhanced response towards thiocyanate from the electrode based on binuclear metallic complex copper (II) [Cu(II)₂–BBSTA] was observed. The electrode based on binuclear copper(II) compound was used to determine the thiocyanate content in waste water with satisfactory results.     

Studies on the interaction between imidacloprid and human serum albumin: Spectroscopic approach

The interaction between imidacloprid (IMI) and human serum albumin (HSA) was investigated using fluorescence and UV/vis absorption spectroscopy. The experimental results showed that the fluorescence quenching of HSA by IMI was a result of the formation of IMI–HSA complex; static quenching was confirmed to result in the fluorescence quenching. The apparent binding constant K_A between IMI and HSA at three differences were obtained to be 1.51 × 10⁴, 1.58 × 10⁴, and 2.19 × 10⁴ L mol^?1, respectively. The thermodynamic parameters, ΔH° and ΔS° were estimated to be 28.44 kJ mol^?1, 174.76 J mol^?1 K^?1 according to the van’t Hoff equation. Hydrophobic interactions played a major role in stabilizing the complex. The distance r between donor (HSA) and acceptor (IMI) was obtained according to fluorescence resonance energy transfer. The effect of IMI on the conformation of HSA was analyzed using synchronous fluorescence spectroscopy CD and three-dimensional fluorescence spectra, the environment around Trp and Tyr residues were altered.     

Potential energy surface and rate constant of the inversion substitution reactions CH3X + O2 → CH3O2• + X• (X = SH,NO2)

The temperature dependence of the rate constant of the inversion substitution reactions CH₃X + O₂ → CH₃O₂^? + X^? (X = SH, NO₂), can be expressed as k = 6.8 × 10^–12(T/1000)^1.49exp(–62816 cal mol^–1/RT) cm³ s^–1 (X = SH) and k = 6.8 × 10^–12(T/1000)^1.26 × × exp(–61319 cal mol^–1/RT) cm³ s^–1 (X = NO₂), as found with the use of high-level quantum chemical methods and the transition state theory.     

A new luminescent sulfate bridged dimeric copper(II) complex with DNA binding and SO2 fixation ability: Synthesis and structure

New luminescent mononuclear and dinuclear copper(II) (S = 1/2) complexes [Cu(HL)(H₂O)₂](ClO₄)₂ (1a) and [Cu₂(HL)₂(μ-SO₄)₂]·2H₂O (1b) were synthesized with the acyclic tridentate pyridine-2-carboxaldehyde-2-pyridylhydrazone ligand, HL (1). Interestingly, the mononuclear complex 1a can be converted into the disulfate bridged dimeric copper(II) complex 1b by passing freshly prepared SO₂ through the basic medium. On excitation at 290 nm, the ligand fluoresces at 364 nm due to an intraligand ¹(π–π1) transition. Upon complexation with copper(II), the emission peak is slightly blue shifted (356 nm, F/F₀ 0.76 for 1a and 354 nm, F/F₀ 0.89 for 1b) with a little quenching in the emission intensity. The association constants (K_ass (5.06 ± 0.004) × 10⁴ for 1a and K_ass (5.46 ± 0.006) × 10⁴ for 1b at 298 K) and the thermodynamic parameters have been determined by UV–Vis spectroscopy. The molecular structure of the complex 1b (Cu?Cu 4.456 Å) has been determined by single crystal X-ray diffraction studies. The complex 1b exhibits a strong interaction towards DNA as revealed from the K_b (intrinsic binding constant) 6.3 × 10⁴ M^?1 and K_sv (Stern–Volmer quenching constant) 2.93 values.     

On the kinetics of thermal electron attachment to perfluoroethers

In this Letter we report the results of the measurements of the rate coefficients for thermal attachment to several perfluoroethers namely perfluorodiglyme (C₆F₁₄O₃), perfluorotriglyme (C₈F₁₈O₄), perfluoropolyether (CF₃–(OCF(CF₃)CF₂)_n–(OCF₂)_m–OCF₃) and perfluorocrownether ((C₂F₄O)₅). Rate coefficients were obtained under thermal conditions in the temperature range 298–378 K. The increase of the rates with temperature follows the Arrhenius law and the activation energies have been obtained from the slope of the ln(k) vs. 1/T. The respective values of the rate coefficients (at 298 K) and activation energies are as follows: 7.7 ± 1.2 × 10^?11 cm³ s^?1 (0.18 ± 0.005 eV), 6.7 ± 2.1 × 10^?11 cm³ s^?1 (0.25 ± 0.004 eV), 2.1 ± 0.2 × 10^?10 cm³ s^?1 (0.16 ± 0.010 eV), 3.1 × 10^?11 cm³ s^?1 (0.27 ± 0.003 eV) for C₆F₁₄O₃, C₈F₁₈O₄, CF₃–(OCF(CF₃)CF₂)_n–(OCF₂)_m–OCF₃ and (C₂F₄O)₅.     

Validated voltammetric method for the determination of some antiprotozoa drugs based on the reduction at an activated glassy carbon electrode

A sensitive electrochemical procedure based on reduction of secnidazole (I), tinidazole (II) and ornidazole (III) at a glassy carbon electrode (GCE) was introduced. A study of the variation of the peak current with solution variables such as pH, ionic strength, concentration of drugs, possible interference, and instrumental variables such as scan rate, pulse amplitude, preconcentration time, accumulation potential, has resulted in the optimization of the reduction signal for analytical purposes. Linear calibration plots were obtained over the concentration ranges of 50–800, 50–750 μg mL^?1 for I, and both (II, III) respectively, in Britton–Robinson buffer of pH 7. The relative standard deviations of five replicate measurements of 1.0 and 10.0 μg mL^?1 of I, II and III concentrations were 4.7%, 4.9% and 5.3%, and 2.2%, 2.6% and 2.8%, respectively. The limits of detection (LOD) for I, II and III were found to be 2 × 10^?10, 3 × 10^?10 and 2.5 × 10^?10 mol L^?1 and limits of quantification (LOQ) for I, II and III were found to be 4.0 × 10^?8, 1.2 × 10^?8 and 4.4 × 10^?8 mol L^?1, respectively. The optimal conditions were: E_acc = ?0.9 V, t_acc = 30 s, scan rate = 20 mV s^?1, pulse-height = 90 mV and Britton–Robinson buffer of pH 7. The method was applied for the determination of the cited drugs both in raw materials and in pharmaceutical preparations with satisfactory results and compared with the official reference method. Complete validation of the proposed method was also done.     

The thioantimonate anion [Sb4S8]4− acting as a tetradentate ligand: Solvothermal synthesis,crystal structure and properties of {[In(C6H14N2)2]2Sb4S8}Cl2 exhibiting unusual uniaxial negative and biaxial positive thermal expansion

The new compound {[In(C₆H₁₄N₂)₂]₂Sb₄S₈}Cl₂ was prepared under solvothermal conditions reacting InCl₃, Sb and S using 1,2-trans-diaminocyclohexane as solvent and structure directing molecule. The compound crystallizes in the monoclinic space group C2/c with a = 29.0259(12), b = 6.7896(2), c = 24.2023(12) Å, β = 99.524(4)°, V = 4703.9(3) ų. The central structural motif is the thioantimonate(III) anion [Sb₄S₈]^4? acting as a tetradentate ligand thus joining two symmetry related In³⁺ centered complexes. This binding mode was never observed before for the [Sb₄S₈]^4? anion. The optical band gap was determined as 2.03 eV in agreement with the red color of the compound. The thermal decomposition was monitored with in-situ X-ray diffraction experiments. After the emission of the amine molecules an amorphous intermediate is formed followed by the crystallization of InSbS₃ which is stable up to about 590 °C. On further heating, InSbS₃ is destroyed and reflections of γ-In₂S₃ appear being contaminated with some elemental Sb. Temperature dependent in-situ X-ray powder diffractometry performed between 30 and 220 °C reveals an unusual reversible negative and positive thermal expansion. The decrease of the a-axis in the temperature range is about 0.74 Å and the increase of the c-axis ca. 0.54 Å. Interestingly, the b-axis exhibits also a thermal expansion, i.e., a biaxial positive and an uniaxial negative thermal expansion coexist which is very unusual. The relative negative expansion coefficients for the a-axis of ?194 × 10^?6K^?1 (30–120 °C) and ?82 × 10^?6K^?1 (120–220 °C) are in the region of so-called colossal thermal expansion.     

A dysprosium nanowire modified carbon paste electrode for determination of levodopa using fast Fourier transformation square-wave voltammetry method

A new detection technique called the fast Fourier transform square-wave voltammetry (FFT-SWV) is based on the measurements of electrode admittance as a function of potential. The response of the detector (microelectrode) is fast, which makes the method suitable for most applications involving flowing electrolytes. The carbon paste electrode was modified by nanostructures to improve better sensitivity. The response is generated by a redox processes. The redox property of L-dopa was used for determination of it in human serum and urine samples. The support electrolyte that provided a more defined and intense peak current for L-dopa determination was at 0.05 mol l^?1 acetate buffer pH 7.0. Synthesized dysprosium nanowires make more effective surface like nanotubes [1], [2], [3], [4] so they are good candidates for using as a modifier for electrochemical reactions. The drug presented one irreversible oxidation peaks at 360 mV versus Ag/AgCl by modified nanowire carbon paste electrode which produced high current and reduced the oxidation potential about 80 mV.Furthermore, signal-to-noise ratio has significantly increased by application of discrete fast Fourier transform (FFT) method, background subtraction and two-dimensional integration of the electrode response over a selected potential range and time window. To obtain the much sensitivity the effective parameters such as frequency, amplitude and pH was optimized. As a result, C_DL of 4.0 × 10^?9 M and an LOQ of 7.0 × 10^?9 M were found for determination for L-dopa. A good recovery was obtained for assay spiked urine samples and a good quantification of L-dopa was achieved in a commercial formulation.     

Electrochemical synthesis of a ferrocenecarboxylic acid–C60 composite and its electrocatalysis to hydrogen peroxide

A new ferrocenecarboxylic acid–C₆₀ composite (Fc–C₆₀) has been synthesized by controlled potential electrolysis. A composite modified glassy carbon electrode has been prepared based on its good electrochemical activity. The modified electrode in 0.1 M NaClO₄ solution shows a reversible oxidation wave at E_1/2 = 0.32 V (vs. SCE) attributed to the oxidation of the ferrocene entity and a quasi-reversible reduction wave of C₆₀ entity at E_1/2 = ?0.54 V (vs. SCE). Electrocatalytic studies show that Fc–C₆₀ at the modified electrode can mediate the reduction of hydrogen peroxide (H₂O₂), and a broad linear range from 1.2 μM to 21.9 mM for H₂O₂ were obtained with a determination limit of 2.5 × 10^?7 M by amperometry.     

Complexation study and spectrofluorometric determination of the binding constant for diquat and p-sulfonatocalix[4]arene

The interactions between diquat (DQ) and p-sulfonatocalix[4]arene (C4S) were studied in an aqueous solution as a function of the ionic strength. Evidence for the formation of a complex between DQ and C4S was obtained using fluorescence measurements, while the stoichiometry of the complex was confirmed as 1:1 for DQ/C4S using UV–vis spectroscopy. The ionic strength had no influence on the stoichiometry of the complex, but exerted a significant influence on the complexation constant, K_c, decreasing with an increase in the ionic strength. The thermodynamic complexation constant, K_c′, was computed as 5.25±1.11×10⁷ using the extended Debye–Hückel law. The rate constants for the heterogeneous electron transfer for the reduction of DQ at an electrode surface were evaluated as 0.150±0.010 cm s^?1 in the absence of C4S and 0.065±0.010 cm s^?1 when C4S was added to the solution in a 1:1 ratio.     

Novel sucrose-based macrocyclic receptors for enantioselective recognition of chiral ammonium cations

A new synthetic route to macrocyclic sucrose-based receptors with different substituents at the ring nitrogen atom is described. Very good enantioselectivity toward phenylethylammonium chloride was observed [a much stronger complex with the cation of the (S)-amine was formed] although the K_a values were low. Much higher K_a (1.4 × 10⁴ M^?1 in CDCl₃/CD₃OD) values of the complexes with aminoacid derivatives (especially valine) were found although this time the enantioselectivities were moderate.     

Synthesis of carbohydrate-functionalized thiophene-capped cyclopenta[c]thiophene for concanavalin A recognition

Synthetic route to two different carbohydrate-functionalized oligothiophenes comprising central cyclopenta[c]thiophene (CPT) moiety was demonstrated. Turbidimetric analysis revealed enhanced interaction for divalent α-mannose-functionalized terthiophene 7 with Con A. The extent of binding interaction for 7-Con A complex formation was determined from isothermal titration calorimetry (ITC) measurements and the binding constant found (K_ITC) 2.4(6) × 10⁵ M^?1.     

Anthracene-based macrocyclic fluorescent chemosensor for selective sensing of dicarboxylate

An anthracene-based macrocyclic receptor has been designed and synthesized for selective recognition of 1,4-phenylenediacetate (K_a = 3.34 × 10⁵ M^?1). The macrocycle binds 1,4-phenylenediacetate selectively at the charged sites of the receptor with a concomitant increase in fluorescence of anthracene. The interaction properties of the macrocycle were evaluated by ¹H NMR, UV–vis and fluorescence spectroscopic methods.     

Flow injection potentiometric sensor for determination of phenylpropanolamine hydrochloride

A new polymeric membrane electrode has been constructed for the determination of phenylpropanolamine hydrochloride. The electrode was prepared by solubilizing the phenylpropanolamine-phosphomolybdate ion associate into a polyvinyl chloride matrix plasticized by dibutylphthalate as a solvent mediator. The electrode showed near-Nernstian response over the concentration range of 1 × 10^?5–1 × 10^?2 M with low detection limit of 6.3 × 10^?6 M. The electrode displays a good selectivity for phenylpropanolamine with respect to a number of common inorganic and organic species. The electrode was successfully applied to the potentiometric determination of phenylpropanolamine ion in its pure state and its pharmaceutical preparation in batch and flow injection conditions.     

S-layer templated bioinspired synthesis of silica

The current understanding of the molecular mechanisms involved in the bioinspired formation of silica structures laid foundation for investigating the potential of the S-layer protein SbpA from Lysinibacillus sphaericus CCM 2177 as catalyst, template and scaffold for the generation of novel silica architectures. SbpA reassembles into monomolecular lattices with square (p4) lattice symmetry and a lattice constant of 13.1 nm. Silica layers on the S-layer lattice were formed using tetramethoxysilane (TMOS) and visualized by transmission electron microscopy. In situ quartz crystal microbalance with dissipation monitoring (QCM-D) measurements showed the adsorption of silica in dependence on the presence of phosphate in the silicate solution and on the preceding chemical modification of the S-layer. An increased amount of precipitated silica could be observed when K₂HPO₄/KH₂PO₄ was present in the solution (pH 7.2). Further on, independent of the presence of phosphate the silica deposition was higher on S-layer lattices upon activation of their carboxyl groups with 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC) compared to native S-layers or EDC treated S-layers when the activated carboxyl groups were blocked with ethylene diamine (EDA). Fourier transform infrared attenuated total reflectance (FTIR-ATR) spectroscopy revealed the formation of an amorphous silica gel (SiO₂)_x·yH₂O on the S-layer. The silica surface concentrations on the S-layer was 4 × 10^?9 to 2 × 10^?8 mol cm^?2 depending on the modification of the protein layer and corresponded to 4–21 monolayers of SiO₂.