Formation Constants Of Complexes Research Articles

Factorial design-aided derivatization-free fluorimetric ultrasensitive assay of vonoprazan with application in uniformity of dosage units and plasma samples analysis: Comprehensive and comparative greenness and whiteness assessment

This study presents a novel derivatization-free spectrofluorimetric method for the quantification of vonoprazan (VPZ) that is characterized by its high sensitivity, environmental friendliness, and cost-effectiveness. Notably, this method eliminates the requirement for pre-derivatization, extraction procedures, large amounts of organic solvents, and/or expensive instrumentation, which distinguishes it from previous approaches. The approach employed in this study relies on the formation of an association complex between VPZand the xanthene dye acid red 87 (AR87) under acidic conditions. The stability of the VPZ-AR87 complex was determined to be remarkably high, with a complex formation constant (Kf) value exceeding 2 x 106 M−1. The fluorimetric measurements rely on the quantitative and selective quenchingof the dye’s native fluorescence emission at 545 nm. The experimental parameters were optimized utilizing a quality-by-design 23 full factorial design. This strategy yielded a highly favorable linearity range of 10.0 to 400.0 ng/mL, with a correlation coefficient (r) of 0.9997. The presented methodology exhibited a high level of sensitivity, as evidenced by its ability to detect concentrations as low as 1.2 ng/mL. This sensitivity enabled its successful application for the estimation of VPZ in human plasma samples with high %recoveries (98.21–101.67) and low %RSD values (<1.52). Furthermore, content uniformity testing of low-dose VPZ tablets was performed according to United States Pharmacopeia guidelines. Greenness and whiteness metrics analysis showed a significant advantage of the proposed method over previously reported fluorimetric methods. Validation of the developed approach was carried out in accordance with ICHQ2 (R1) guidelines.

Sorption of picolinic acid by Cu(II)-containing sulfocationite KU-2-8

Objectives. To study the equilibrium distribution of components between KU-2-8 sulfocationite and an aqueous solution containing picolinic acid and Cu(II); to show the possibility of immobilization of cations of picolinic acid and Cu2+ in sulfonic cation exchanger KU-2-8; to calculate the component compositions of the equilibrium solution, in order to obtain the required ionic composition of the KU-2-8 sulfonic cation exchanger according to the selectivity coefficients of binary ion exchange, and the constants of formation of such complexes in water.Methods. The concentrations of the individual components in multicomponent solutions were calculated using the HySS 2009 program (Hyperquad Simulaton and Speciation). The calculation of the equilibrium ionic compositions of KU-2-8 sulfocationite was performed using the selectivity coefficients of binary ion exchanges and the formation constants of complexes of picolinic acid with Cu2+ and H+ cations. Experimental study of the equilibrium distribution of components between aqueous solutions of picolinic acid, copper nitrate, and KU-2-8 sulfocationite was carried out by means of the dynamic method at a temperature of 298 K. Fourier-transform infrared spectroscopy and electron paramagnetic resonance spectroscopy were used, in order to determine the ionic forms of the components contained in the sulfocationite.Results. It was shown that the equilibrium solution contains H+ protons, Cu2+ cations, LH picolinic acid molecules, protonated picolinic acid cations [H2L]+, deprotonated picolinic acid anions L-, Cu2+ complexes with the deprotonated picolinic acid anion [CuL]+, and Cu2+ complexes with two anions of deprotonated picolinic acid [CuL2]. The concentration of H+, Cu2+, and [H2L]+ cations in the solution significantly exceeds the concentration of other components at pH values from 0 to 0.5. The content of [CuL]+ cations and neutral complexes [CuL2] increases significantly in the solution, while the [H2L]+ cations disappear at pH greater than 1. It was experimentally established that the concentrations of picolinic acid and copper in the polymer phase are many times higher than the concentrations of these components in an aqueous solution. The partition coefficients are about 24 and 210 for picolinic acid and Cu(II), respectively. The calculated dependencies of the concentrations of Cu2+, [H2L]+, H+, [CuL]+ cations in the polymer vs pH of an equilibrium solution containing picolinic acid were obtained. The experimental data on the concentrations of all cations in the ion exchanger is in the intervals of the calculated compositions within the limits of measurement errors.Conclusions. KU-2-8 sulfocationite is proposed as a container for obtaining drugs based on picolinic acid and Cu2+ cations. It was shown that the selectivity coefficients of binary ion exchanges and the formation constants of [H2L]+, [CuL]+ complexes can be used to precalculate the ionic compositions of the equilibrium solution, in order to obtain the required compositions of the sulfocationite.

Thermodynamics of complex formation of silver(I) with substituted pyridines and cyclic amines in non-aqueous solvents

The understanding of the thermodynamic stability and speciation of metal complexes in solution requires access to their enthalpy and entropy of formation. In this work, we specifically focus our investigation on the complexation process of silver(I) ion in acetonitrile (AN) with substituted mono pyridines and cyclic monoamines. The aim of this study is to provide reliable thermodynamic data to obtain insights on metal complex formation, focusing on ligands donor properties and solvation effects. Carefully designed potentiometric and calorimetric experiments allowed to define the species present at different ligand/metal ratios and to obtain the complex formation constants and enthalpies. In general, the enthalpy terms associated with the complex formation are highly exothermic, while the entropy values are always unfavorable. The formation constants of AgLj species for the ligands investigated in AN are compared with those previously obtained in dimethyl sulfoxide (DMSO) and water. The trends in stability constants and enthalpy values are discussed in relation to the pKa data available in the different solvents. Higher pKa values correspond to greater ligand basicity and result in more stable and more enthalpy stabilized complexes.

Cyclodextrin-enhanced photo-induced fluorescence of tau-fluvalinate, molecular modelling of inclusion complexes and determination in natural waters.

The effect of adding organized supramolecular systems such as β-cyclodextrin (β-CD) and hydroxypropyl-β-cyclodextrin (HP-β-CD) on the photochemically-induced fluorescence (PIF) spectral properties of tau-fluvalinate (TFV) in aqueous solutions was examined. The influence of pH, UV irradiation time and photoproduct stability on the cyclodextrin-enhanced photochemically-induced fluorescence intensity was also investigated. The spectral changes associated with the inclusion process yielded values for the formation constants of TFV inclusion complexes between 450 and 640 M-1, which were calculated using the nonlinear iterative regression approach least squares. In addition, host-guest interaction was clearly determined by PIF enhancement and a 1 : 1 stoichiometry was found for the β-CD and HP-β-CD complexes formed with TFV. The negative free energy (ΔG°) value indicated that the reaction of TFV with cyclodextrins was thermodynamically favorable. Furthermore, the structures of inclusion complexes of TFV with cyclodextrins were elucidated by 3-21G ab initio calculations. The limits of detection and quantification obtained ranged between 1.3 and 4.0 ng mL-1 and from 4.4 to 13.0 ng mL-1 in β-CD and HP-β-CD media, respectively. The analytical application in tap and river water samples yielded satisfactory mean recoveries ranging from 98.12 to 102.97%. Due to its sensitivity and ease of use, this method can be reliably applied to routine analysis.

Protonation constants of endo- and exogenous L-amino acids and their derivatives in aqueous and mixed solution: Unraveling molecular secrets.

The aim of this review is to summarize the progress made in the determination of the protonation constants of biologically active ligands: endo- and exogenous L-amino acids and their derivatives in aqueous and mixed solutions using different experimental techniques. The knowledge of the protonation constants of the aforementioned ligands is crucial for the determination of the equilibrium constants of complex formation and thus for the understanding of complex biological reactions such as transamination, racemization, and decarboxylation. Thus, the protonation constants of ligands are a measure of their ability to form complexes with metal ions. This knowledge not only helps to understand fundamental biochemical processes, but also has practical applications in areas such as drug design, where ligands are often targeted for therapeutic purposes. The activity of the ligands tends to increase after complexation and their order is consistent with the values of the stepwise dissociation constants of the complexes formed. Understanding the properties of ligands by determining their protonation constants in different environments and their interactions with surrounding molecules is crucial to unraveling the complexity of biological systems.

ТЕРМОДИНАМИКА КОМПЛЕКСООБРАЗОВАНИЯ И СТРУКТУРА КОМПЛЕКСОВ ЦИНКА(II) С ГИСТИДИНОМ И 2-МЕТИЛДИПИРИДОХИНОКСАЛИНОМ

The complex formation in the zinc(II) - 2-methyldipyrido-[3,2-f:2',3'-h]-quinoxaline (MeDPQ), zinc(II) - L-histidine (HisH) and zinc(II) - 2-methyldipyrido-[3,2-f:2',3'-h]-quinoxaline - L-histidine systems at 37.0 °C on the 0.15 mol dm-3 NaCl background has been investigated by the pH-potentiometry method. A total of 10 complex forms were characterized. Based on the analysis of the complex formation constants and DFT calculations at the B3LYP/TZVPP level, taking into account the solvent effect within the C-PCM model, the structures of Zn(MeDPQ)(HisH)2+, Zn(MeDPQ)(His)+, and Zn(MeDPQ)(His)(OH) complexes were modeled. The higher stability of the homoligand complexes Zn(His)+, Zn(HisH)(His)+, Zn(His)2 and extra-stabilization in the formation constants of the heteroligand complexes Zn(MeDPQ)(HisH)2+ and Zn(MeDPQ)(His)+ were discovered, which was confirmed by the DFT calculations. Higher values of equilibrium constants of the mentioned homoligand forms are explained by coordination to the central nitrogen atom of the imidazole fragment of histidine. Extra-stabilization of heteroligand forms occurs due to d-π-interaction with electron density transfer from π-donor orbitals of oxygen atoms of the carboxy groups of amino acids through the central ion to π-acceptor orbitals of MeDPQ. It is emphasized that the studied zinc(II) complexes, both in binary and ternary systems, can have high biological activity, in particular, due to the nucleophilic attack of the coordinated hydroxide anion on proteins and other biomaterials. This opens up the prospect of using such zinc(II) complexes in medicine. In particular, the studied complexes may exhibit anticancer activity.

Immobilization of technetium by iron corrosion phases: lessons learned and future perspectives

Abstract. Technetium-99 (99Tc) is a long-lived fission product (2.13×105 years) of uranium-235 (235U) and plutonium-239 (239Pu) and, therefore, of great concern for the long-term safe management of nuclear waste. The migration of Tc in the environment is highly influenced by the redox conditions, since Tc may be present in various oxidation states. Depending on the chemical properties of environmentally relevant systems, Tc is expected to mainly occur as Tc(VII) and as Tc(IV) under oxidizing and reducing conditions, respectively. The anion pertechnetate (Tc(VII)O4-) is known to barely interact with mineral surfaces; this, in turn, enhances its migration in groundwater and favors its entry into the biosphere. On the contrary, the formation of Tc(IV) limits the migration of Tc, since it forms a low soluble solid (TcO2) and/or species, whose interaction with minerals is more favorable. In the last few decades Tc migration has been focused on the reduction of Tc(VII) to Tc(IV) by various reductants, such as Fe(II), Sn(II), or S(-II), which are either present in solution, taking part in mineral structures (Pearce et al., 2019), or metabolically induced by microbial cascades (Newsome et al., 2014). We have studied the immobilization of technetium (Tc) by various Fe(II)-containing phases, including Fe2+ pre-sorbed on alumina nanoparticles (Mayordomo et al., 2020), Fe(II)-Al(III)-layered double hydroxide (Mayordomo et al., 2021), and Fe(II) sulfides (Rodríguez et al., 2020; Rodríguez et al., 2021). We have combined sorption experiments with microscopic and spectroscopic techniques (scanning electron microscopy, Raman microscopy, X-ray photoelectron spectroscopy, infrared spectroscopy, and X-ray absorption spectroscopy) to elucidate the mechanisms responsible for Tc(VII) reductive immobilization. Those works have been focused on binary systems (i.e., studies of the interaction of Tc with a given reductant). However, the environment is a complex system, where different components often depend on and modify each other. Thus, Tc migration is susceptible and varies, depending on environmental conditions, and should not be studied in an isolated manner. The young investigator group TecRad (HZDR, 2022), funded by the German Federal Ministry of Education and Research, aims at analyzing Tc chemistry from a wider perspective. Our goal is to study the biogeochemical behavior of Tc when it interacts with (i) microorganisms, (ii) metabolites, (iii) Fe(II) minerals, and (iv) Fe(II) minerals in presence of metabolites. An important part of this project deals with implementing new spectro-electrochemical methods to monitor the in situ the behavior of Tc in solution and at interfaces as a function of the redox potential. With these tools, we aspire to characterize the molecular structures of Tc species under a variable range of redox conditions to broaden the understanding of the chemical behavior of the pollutant. We aim at generating valuable thermodynamic data (complex formation constants, solubility constants of minerals, redox potentials, and Tc distribution coefficients) that will be used to implement a geochemical modeling able to explain Tc's environmental fate, even under different redox conditions.

Association thermodynamics parameters of nano vanadyl sulphate and its complexes with Orange G at different temperatures, docking versus Covid-19 and antioxidant behavior

Molecular thermodynamic association parameters for the bulk and nano-vanadyl sulfate were determined by the conductometry in aqueous solution at various temperatures. The thermodynamic parameters for complex formation 1:1, 1:2 (M/L) between bulk & nano vanadyl with Orange G were also determined by the conductivity measurements. From the interaction of the bulk & nano vanadyl sulfate (VOSO4) with Orange G, in the instance of the 1:1 complex as opposed to the 1:2 (VOSO4/Orange G) complex in water as the solvent, the estimated Kf and ΔGf were higher. When the temperature rises, the complex formation constants decrease. The molecular complexation's negative ΔGf values show that the production of molecular complexes is spontaneous and that it gets higher as the temperature rises. The molecular complexation is an endothermic and entropy-controlled reaction, which is supported by the negative values of ΔHf. Molecular docking of vanadyl sulfate versus 7 jwy of amino acid of covid-19 allows us to better understand the probable modes of engagement and binding affinities of the targeted molecule (vanadyl sulfate), that provide more clarity on how well the molecules exert bioactivity towards the target. The vanadyl sulfate show greater antioxidant behavior than the stander ascorbic acid with the same concentration. Also, the oxygen radicals ranging from 1.1 to 1.4 V which are reduced giving reduction peaks (broad) facilitating the use of vanadyl sulfate as a strong antioxidant solution.

Macrocyclic 1,2-Hydroxypyridinone-Based Chelators as Potential Ligands for Thorium-227 and Zirconium-89 Radiopharmaceuticals.

Thorium-227 (227Th) is an α-emitting radionuclide that has shown preclinical and clinical promise for use in targeted α-therapy (TAT), a type of molecular radiopharmaceutical treatment that harnesses high energy α particles to eradicate cancerous lesions. Despite these initial successes, there still exists a need for bifunctional chelators that can stably bind thorium in vivo. Toward this goal, we have prepared two macrocyclic chelators bearing 1,2-hydroxypyridinone groups. Both chelators can be synthesized in less than six steps from readily available starting materials, which is an advantage over currently available platforms. The complex formation constants (log βmlh) of these ligands with Zr4+ and Th4+, measured by spectrophotometric titrations, are greater than 34 for both chelators, indicating the formation of exceedingly stable complexes. Radiolabeling studies were performed to show that these ligands can bind [227Th]Th4+ at concentrations as low as 10-6 M, and serum stability experiments demonstrate the high kinetic stability of the formed complexes under biological conditions. Identical experiments with zirconium-89 (89Zr), a positron-emitting radioisotope used for positron emission tomography (PET) imaging, demonstrate that these chelators can also effectively bind Zr4+ with high thermodynamic and kinetic stability. Collectively, the data reported herein highlight the suitability of these ligands for use in 89Zr/227Th paired radioimmunotheranostics.

Characterization of thermodynamic properties on Al3+/dopamine system

The interactions of dopamine (Dop−) with aluminum were studied in NaCl(aq) at different ionic strengths (0.15 ≤ I/mol dm−3 ≤ 1.0) and temperatures (288.15 ≤ T/K ≤ 310.15). The investigations were carried out by using ISE-[H+] potentiometry, UV–Vis spectrophotometry and 1H NMR. The results obtained from the different techniques were in good agreement, both in terms of speciation model and stability constants of the complexes. The speciation model is featured by mononuclear complexes, namely: AlDop; AlDopOH; AlDop(OH)2 and AlDop(OH)3 (charges omitted). From 1H NMR investigations, it resulted that both the amino and the phenolic groups in meta position of aromatic ring are involved in the protonation equilibria, while the Al3+ complexation occurs from the catechol side of the ligand. The dependence on the ionic strength and temperature of the complex formation constants was modelled by a modified extended Debye-Hückel equation, containing a term for the dependence on T/K. The SIT approach allowed the calculation of the specific ion interaction coefficients of the aluminum:dopamine complexes. From the enthalpy change values obtained, it resulted that the formation of the species is exothermic in nature and that the entropy is the driving force of the processes. The sequestering ability of dopamine towards Al3+ was evaluated by the calculation of pL0.5 parameter at different ionic strengths, pHs and temperatures; the dependence of the pL0.5 on these variables was modelled by using an empirical predictive equation that allows the calculation of the effective sequestering ability of dopamine at desired conditions. The precipitates collected at the end of the potentiometric titrations were studied by means of thermogravimetric (TGA) analysis.

Eu(III) and Cm(III) Complexation by the Aminocarboxylates NTA, EDTA, and EGTA Studied with NMR, TRLFS, and ITC-An Improved Approach to More Robust Thermodynamics.

The complex formation of Eu(III) and Cm(III) was studied via tetradentate, hexadentate, and octadentate coordinating ligands of the aminopolycarboxylate family, viz., nitrilotriacetate (NTA3-), ethylenediaminetetraacetate (EDTA4-), and ethylene glycol-bis(2-aminoethyl ether)-N,N,N',N'-tetraacetate (EGTA4-), respectively. Based on the complexones' pKa values obtained from 1H nuclear magnetic resonance (NMR) spectroscopic pH titration, complex formation constants were determined by means of the parallel-factor-analysis-assisted evaluation of Eu(III) and Cm(III) time-resolved laser-induced fluorescence spectroscopy (TRLFS). This was complemented by isothermal titration calorimetry (ITC), providing the enthalpy and entropy of the complex formation. This allowed us to obtain genuine species along with their molecular structures and corresponding reliable thermodynamic data. The three investigated complexones formed 1:1 complexes with both Eu(III) and Cm(III). Besides the established Eu(III)-NTA 1:1 and 1:2 complexes, we observed, for the first time, the existence of a Eu(III)-NTA 2:2 complex of millimolar metal and ligand concentrations. Demonstrated for thermodynamic studies on Eu(III) and Cm(III) interaction with complexones, the utilized approach is commonly applicable to many other metal-ligand systems, even to high-affinity ligands.

Stability of the Inclusion Complexes of Dodecanoic Acid with α-Cyclodextrin, β-Cyclodextrin and 2-HP-β-Cyclodextrin

In the presented work, the stability of the formation of inclusion complexes of dodecanoic acid (lauric acid) with three cyclodextrins, α-cyclodextrin, β-cyclodextrin and 2-HP-β-cyclodextrin, was analyzed from the point of view of the size of the cavity in cyclodextrins, their molar mass and the structure of the studied fatty acid. The measurements were made in a wide temperature range of 283.15-318.15K. The conductometric method was used for these studies. The results obtained allowed us to determine the value of the theoretical limiting molar conductivity (Λm0) of the studied complexes, the values of the inclusion complex formation constants (Kf) and the values of thermodynamic functions (ΔG0, ΔH0 and ΔS0) describing the complexation process in the studied temperature range.

Half-Sandwich Rhodium Complexes with Releasable N-Donor Monodentate Ligands: Solution Chemical Properties and the Possibility for Acidosis Activation.

Cancer chemotherapeutics usually have serious side effects. Targeting the special properties of cancer and activation of the anticancer drug in the tumor microenvironment in situ may decrease the intensity of the side effects and improve the efficacy of therapy. In this study, half-sandwich Rh complexes are introduced, which may be activated at the acidic, extracellular pH of the tumor tissue. The synthesis and aqueous stability of mixed-ligand complexes with a general formula of [Rh(η5-Cp*)(N,N/O)(N)]2+/+ are reported, where (N,N/O) indicates bidentate 8-quinolate, ethylenediamine and 1,10-phenanthroline and (N) represents the releasable monodentate ligand with a nitrogen donor atom. UV-visible spectrophotometry, 1H NMR, and pH-potentiometry were used to determine the protonation constants of the monodentate ligands, the proton dissociation constants of the coordinated water molecules in the aqua complexes, and the formation constants of the mixed-ligand complexes. The obtained data were compared to those of the analogous Ru(η6-p-cymene) complexes. The developed mixed-ligand complexes were tested in drug-sensitive and resistant colon cancer cell lines (Colo205 and Colo320, respectively) and in four bacterial strains (Gram-positive and Gram-negative, drug-sensitive, and resistant) at different pH values (5-8). The mixed-ligand complexes with 1-methylimidazole displayed sufficient stability at pH 7.4, and their activation was found in cancer cells with decreasing pH; moreover, the mixed-ligand complexes demonstrated antimicrobial activity in Gram-positive and Gram-negative bacteria, including the resistant MRSA strain. This study proved the viability of incorporating releasable monodentate ligands into mixed-ligand half-sandwich complexes, which is supported by the biological assays.

Single-Hydroxide Bridged Dimers of U and Np Actinyls: A Density Functional Study on Their Existence and Structure in Aqueous Solution

With quantum chemical calculations at the density functional theory level, we examined the structure and the stability of diactinyl monohydroxo complexes [(AnO2)2(OH)]3+/+ in aqueous solution for An = U(VI), Np(VI), and Np(V). In particular, this study contributes to understanding the hydrolysis of Np(VI) and Np(V), which is less well characterized than for U(VI). [(UO2)2(OH)]3+ is a known hydrolysis complex of U(VI) at low pH. Although not yet found in experiments, [(NpO2)2(OH)]3+ is suggested to exist due to the similarity between Np(VI) and U(VI) complexes, while [(NpO2)2(OH)]+ is a hypothetical species thus far. Our calculations suggest that the An(VI) complexes favor the parallel orientation of actinyls, whereas for the Np(V) complex a perpendicular arrangement is stabilized by hydrogen bonds between aqua ligands and the actinyl oxygen atoms. The Np(VI) complex [(NpO2)2(OH)]3+ features a structure and stability similar to its U(VI) analogue. From calculated formation constants for An(VI) diactinyl monohydroxo complexes, we find qualitative agreement with the experiment for U(VI). Both An(VI) complexes are only slightly less stable than the separate mononuclear constituents, the actinyl aqua and the monohydroxo complex. For the Np(V) species [(NpO2)2(OH)]+, we calculated a considerably lower complexation constant than for its An(VI) analogues, but it is more stable against decay into its constituents. Thus, this complex may exist at about the pH where Np(V) hydrolysis starts at not too low Np(V) concentrations.

Development of a Transcriptional Activator-Like Effector Protein to Accurately Discriminate Single Nucleotide Difference.

Transcriptional activator-like effector (TALE), a DNA-binding protein, is widely used in genome editing. However, the recognition of the target sequence by the TALE is adversely affected by the number of mismatches. Therefore, the association constant of DNA-TALE complex formation can be controlled by appropriately introducing a mismatch into the TALE recognition sequence. This study aimed to construct a TALE that can distinguish a single nucleotide difference. Our results show that a single mismatch present in repeats 2 or 3 of TALE did not interfere with the complex formation with DNA, whereas continuous mismatches present in repeats 2 and 3 significantly reduced association with the target DNA. Based on these findings, we constructed a detection system of the one nucleotide difference in gene with high accuracy and constructed a TALE-nuclease (TALEN) that selectively cleaves DNA with a single mismatch.

Recovery of Palladium Metal with High Purity by Selective Reduction from Inorganic Acid Leaching Solutions of Cemented Zinc

A small amount of Pd(II) present in spent electroplating solutions is concentrated by cementation. In this work, a process was developed to recover pure palladium metal by selective reduction from the hydrochloric and the sulfuric acid leaching solutions of cemented zinc. For this purpose, hydrazine and ascorbic acid were employed as reducing agents and the effect of several variables such as the acidity of the leaching solutions, molar ratio of reducing agents to Pd(II), reaction time and temperature was investigated. Since neither of the reducing agents can reduce Pd(II) from strong acidic solutions, it was necessary to decrease the acidity of the leaching solutions by dilution with distilled water. Our results indicated that it was possible to recover Pd metal with high purity by selective reduction after diluting the hydrochloric and sulfuric acid leaching solutions of cemented zinc with distilled water. When the molar ratios of the reducing agents to Pd(II) were the same, the reduction percentage of Pd(II) from the sulfuric acid solution was higher than that from the hydrochloric acid solution, due to the much higher complex formation constant of PdCl42- than Pd(SO4)22-. The reduction of Pd(II) by hydrazine occurred within 15 mins at room temperature, while a higher temperature (60 oC) and longer reaction time (1h) were necessary to reduce Pd(II) with ascorbic acid. The reduction of Pd(II) from sulfuric acid solution was more efficient than from hydrochloric acid solution. It was possible to recover Pd metal with high purity from the leaching solution of cemented zinc using the reduction method.

Entropy and Enthalpy Effects on Metal Complex Formation in Non-Aqueous Solvents: The Case of Silver(I) and Monoamines.

Access to the enthalpy and entropy of the formation of metal complexes in solution is essential for understanding the factors determining their thermodynamic stability and speciation. As a case study, in this report we systematically examine the complexation of silver(I) in acetonitrile (AN) with the following monoamines: n-propylamine (n-pr), n-butylamine (n-but), hexylamine (hexyl), diethylamine (di-et), dipropylamine (di-pr), dibutylamine (di-but), triethylamine (tri-et) and tripropylamine (tri-pr). The study shows that the complex stabilities are quite independent of the length of the substitution chain on the N atom and demonstrates that, in general, the overall enthalpy terms associated with the complex formation are strongly exothermic, whereas the entropy values oppose the complex formations. In addition, we examined the similarity of the formation constants of AgL complexes of the primary monoamines in AN, dimethylsulfoxide (DMSO) and water, which were unexpected on the basis of the difference between the donor properties of solvents.

Analysis of complexation between new bidentate bis-NHC ligand and some metal cations at different temperature

In this research, the determination and complexation process between 3,3'-(2,2'-(4-methyl-phenylenesulfonamido)bis(ethane-2,1-diyl))bis(1-benzyl-3H-benzo[d]imidazol-1-ium)dibromide with Ni2+, Zn2+, Pd2+, Ag+, and Hg2+ cations in the binary mixture of methanol (MeOH) and water (H2O) at different temperatures (15, 25, 35 and 45ºC) were studied using a conductometric method. The results show that the stoichiometry of the complexes in all binary mixed solvents for Ni2+, Zn2+, and Pd2+ were 1:1 (M:L), while in other cases 1:2 (M:L) and 2:1(M:L). The stability constants (log ) of complex formation have been determined by fitting molar conductivity curves using a computer program (GENPLOT). The obtained data shows that in the pure methanol solvent system, the stability order is Ni2+&lt; Pd2+&lt;Zn2+&lt;Hg2+&lt;Ag+ and the complexation process seems more stable in pure methanol in most cases. The thermodynamic parameters were determined conductometrically. The complexes in all cases were found to be enthalpy destabilized but entropy stabilized. The experimental data was tested by using an artificial neural network (ANN) program and was in good agreement with the estimated data.

Study of A Tridentate Schiff-Base as A Highly Selective Fluorescent Sensor for Detection of Copper and Chromium Ions

A simple and easily synthesized fluorescent sensor, Schiff base sensor (SBS), produced by condensation reaction of equal amounts of anthranilic acid and salicyladehyde. It was synthesized and characterized systemically. Both UV-vis and fluorescence spectroscopic studies indicated that the SBS sensor showed good selectivity toward the studied ions: Na+, K+, Cu2+, Co2+, Fe3+ , Al3+ and Cr3+. Whereas, chromium (III) and copper (II) exhibited the largest fluorescence enhancement over the other investigated ions. Chelation-enhanced fluorescence were shown upon the interaction of SBS sensor with some metal ions studied forming inclusion complexes. The fluorescent sensor in aqueous ethanolic solution exhibited high selectivity towards Cu2+ and Cr3+ ions, forming 2 : 1 (L : M) complex as determined by Job’s plot. The formation constants of the inclusion complexes (Mn+/SBS) were measured via spectrofluorometric method applying Benesi-Hildebrand equation.

On the Curcumin and β‐Cyclodextrin Interaction in Aqueous Media. Spectrophotometric and Electrochemical Study

AbstractIt is shown from UV/Vis spectrophotometry measurements, that up to two inclusion complexes between curcumin and β‐cyclodextrin, namely H3Cur(β‐CD) and H3Cur(β‐CD)2, can be formed in aqueous solution at pH=3.6, where the fully protonated and neutral species of curcumin, H3Cur, predominate depending on the β‐CD concentration. The thermodynamic formation constants of these supramolecular complexes were determined and the molar absorptivity coefficients of H3Cur, H3Cur(β‐CD) and H3Cur(β‐CD)2 species were assessed. In the absence of β‐CD, curcumin degradation increases linearly with time at a rate of 3.25 % min−1. However, in its presence, the rate drastically diminishes to 0.11 % min−1. These results were corroborated from independent electrochemical measurements using a bare carbon paste electrode. At 0.01 M β‐CD the first voltammogram cycle displayed single anodic and cathodic peaks while the second cycle is formed by two anodic peaks and one cathodic, all of them being due to single‐electron adsorption‐controlled processes. The current of these peaks can be used to quantify curcumin concentration in real samples.