Thermodynamic Stability Of Complexes Research Articles

In Silico Analysis of the Effect of Hydrastis canadensis on Controlling Breast Cancer.

Background and Objectives: Breast cancer is a significant type of cancer among women worldwide. Studies have reported the anti-carcinogenic activity of Hydrastis Canadensis (Goldenseal) in cancer cell lines. Hydrastis Canadensis could help eliminate toxic substances due to its anti-cancer, anti-inflammatory, and other properties. The design phase includes the identification of potential and effective molecules through modern computational techniques. Objective: This work aims to study Hydrastis Canadensis's effect in controlling hormone-independent breast cancer through in-silico analysis. Materials and Methods: The preliminary screening of reported phytochemicals includes biomolecular networking. Identifying functionally relevant phytochemicals and the respective target mutations/genes leads to selecting 3D proteins of the desired mutations being considered the target. Interaction studies have been conducted using docking. The kinetic and thermodynamic stability of complexes was studied through molecular dynamic simulation and MM-PBSA/GBSA analysis. Pharmacodynamic and pharmacokinetic features have been predicted. The mechanism-wise screening, functional enrichment, and interactional studies suggest that canadaline and Riboflavin effectively interact with the target proteins. Results: Hydrastis Canadensis has been identified as the effective formulation containing all these constituents. The phytoconstituents; Riboflavin and Canadensis showed good interaction with the targets of hormone-independent breast cancer. The complexes were found to be kinetically and thermodynamically stable. Conclusions: Hydrastis Canadensis has been identified as effective in controlling 'hormone-independent or basal-like breast cancer' followed by 'hormone-dependent breast cancer: Luminal A' and Luminal B.

The solution thermodynamic stability of desferrioxamine B (DFO) with Zr(IV)

Desferrioxamine B (DFO, [H4L]+, ligand) is currently the preferred chelator for 89Zr(IV), however the biological studies suggest that it releases the metal ion in vivo. Herein, we present the solution thermodynamics of complexes formed between Zr(IV) and this hexadentate chelating agent, the data surprisingly not yet available in the literature. Several techniques including electrospray ionization mass spectrometry (ESI-MS), potentiometry, UV–Vis spectroscopy and isothermal titration calorimetry (ITC) were used to determine the stoichiometry and thermodynamic stability of complexes formed in solution over pH range 1–11, overcoming all the difficulties with the characterisation of the aqueous solution chemistry of Zr(IV) complexes, like strong hydrolysis and lack of spectral information. A model containing only mononuclear complexes, i.e. [ZrHL]2+ [ZrL]+, [ZrLH−1] throughout the entire measured pH range is proposed. The stability constants and pM (Zr(IV)) value determined for Zr(IV)-DFO system, place DFO among good Zr(IV) chelators, however the formation of 6-coordinate unsaturated complexes (i.e. with coordination sphere of 8-coordinate Zr(IV) completed by water molecules), together with the susceptibility of coordinated water molecule to deprotonation, are suggested to be the reason of in vivo instability of 89Zr(IV)-DFO complexes.

Kinetics and thermodynamics of the reaction of iminodiacetate copper(II) complexes with 1,10-phenanthroline and 2,2′-bipyridine in aqueous, anionic, cationic and nonionic surfactants solutions

The kinetics and thermodynamics have been studied for the reactions of the copper(II) complexes with iminodiacetate (ida), 2,2′-bipyridine (bipy) and 1,10-phenanthroline (phen) as ligands. The kinetics of substitution reactions of two aqua ligands for bipy and phen in the [Cu(ida)(H2O)2] coordination compound has been studied in water and three type of aqueous solutions of the following surfactants: anionic sodium dodecyl sulfate (SDS), cationic hexadecyl trimethyl-ammonium bromide (CTAB) and nonionic t-octylphenoxypolyetoxyethanol (Triton X-100). The progress of the substitution reactions in the studied solutions was monitored spectrophotometrically using the stopped-flow method. The studies have allowed the determination of the effect of the type of surfactant solutions on the rate of the substitution reaction. Moreover, the order of studied reactions has been determined. The research performed has also allowed us to propose the reaction mechanism of the [Cu(ida)(H2O)2] binary complex with chelate ligands (bipy or phen). In addition, the thermodynamic stability of complexes under study in aqueous solutions has been examined using the potentiometric titration method. Moreover, the potential scavenging activity of the copper(II) complexes has been investigated towards the superoxide radical.

Copper(II) ions interactions in the systems with triamines and ATP. Potentiometric and spectroscopic studies

The mode of interaction and thermodynamic stability of complexes formed in binary and ternary Cu(II)/ATP/triamines systems were studied using potentiometric and spectroscopic (NMR, EPR, UV–Vis) methods. It was found that in binary metal-free systems ATP/HxPA species are formed (PA: Spd=spermidine or 3,3-tri=1,7-diamino-4-azaheptane) where the phosphate groups from nucleotides are preferred negative centers and protonated amine groups of amines are positive centers of reaction. In the ternary systems Cu/ATP/Hx(PA) as well as Cu/(ATP)(PA) species are formed. The type of the formed Cu(II) complexes depends on pH of the solution. For a low pH value the complexation appears between Cu(II) and ATP molecules via oxygen atoms of phosphate groups. For a very high pH value, where ATP is hydrolyzed, the Cu(II) ions are bound to the nitrogen atoms of polyamine molecules. We did not detect any direct coordination of the N7 nitrogen atom of adenosine to Cu(II) ions. It means that the CuN7 interaction is an indirect type and can be due to noncovalent interplay including water molecule. EPR studies were performed at glassy state (77K) after a fast freezing both for binary and ternary systems. The glassy state EPR spectra do not reflect species identified in titration studies indicating significant effect of rapid temperature decrease on equilibrium of Cu(II) complexes. We propose the molecular structure of all the studied complexes at the glassy state deduced from EPR and optical spectroscopy results.

Pentavalent Neptunyl ([O≡Np≡O]+) Cation–Cation Interactions in Aqueous/Polar Organic Mixed-Solvent Media

Bonding interactions between polyvalent cations and oxo-anions are well known and characterized by predictably favorable Gibbs energies in solution-phase coordination chemistry. In contrast, interactions between ions of like charge are generally expected to be repulsive and strongly influenced by cation solvation. An exception to this instinctive rule is found in the existence of complexes resulting from interactions of pentavalent actinyl cations ([O≡An≡O]+) with selected polyvalent cations. Such cation–cation complexes have been known to exist since the 1960s, when they were first reported by Sullivan and co-workers. The weak actinyl cation–cation complex, resulting from a bonding interaction between a pentavalent linear dioxo actinyl cation donor and hexavalent actinyl or trivalent/tetravalent metal cation acceptor, has been most commonly seen in media in which water activities are reduced, principally highly-salted aqueous media. Such interactions of pentavalent actinides are of relevance in ongoing research that focuses on advanced nuclear fuel processing systems based on the upper oxidation states of americium. This investigation focuses on exploring the thermodynamic stability of complexes between selected highly-charged metal cations (Al3+, Sc3+, Cr3+, Fe3+, In3+ and $$ {\text{UO}}_{2}^{2 + } $$ ) and the pentavalent neptunyl cation ( $$ {\text{NpO}}_{2}^{ + } $$ , whose coordination chemistry is similar to that of $$ {\text{AmO}}_{2}^{ + } $$ while exhibiting significantly greater oxidation state stability) in aqueous–polar organic mixed-solvents. The Gibbs energies for the cation–cation complexation reactions are correlated with general features of electrostatic bonding models; the $$ {\text{NpO}}_{2}^{ + } \cdot {\text{Cr}}^{3 + } $$ complex exhibits unexpectedly strong interactions that may indicate significant covalency in the cation–cation bonding interaction.

Solution state and complexing ability of 1,4-bis(amidomethylsulfinyl)butane toward iron(III), copper(II), cobalt(II), nickel(II), and manganese(II)

The solution state and thermodynamic stability of complexes of the new antituberculosis agent 1,4-bis(amidomethylsulfinyl)butane (L) with iron(III), copper(II), cobalt(II), nickel(II), and manganese(II) in an aqueous solution in the presence and in the absence of the nonionic surfactant Brij 35 were studied by spectrophotometry, pH potentiometry, NMR relaxation technique (T = 25 °C; variable ionic strength), and mathematical simulation. The geometry optimization of all structures was carried out by the molecular mechanics method MM2 in order to obtain data on coordination modes. In addition, the structure of 1,4-bis(amidomethylsulfinyl)butane was refined by the DFT/B3LYP/6-311++G(d,p) quantum chemical method using the IEFPCM model to take into account solvent effects. In an aqueous solution (in the concentration range of 1.3•10–5—1•10–3 mol L–1) and in the presence of Brij 35, 1,4-bis(amidomethylsulfinyl)butane exists as a neutral monomer. The Beer—Lambert—Bouguer law is obeyed in a wide concentration range for compound L in an aqueous solution, as well as in the presence of the surfactant, which can be used for the quantification of compound L. Iron(III), cobalt(II), and nickel(II) were shown to form 1: 1 mononuclear complexes with L; and copper(II) forms, 1: 1 and 2: 2 complexes. The presence of Brij 35 in the Cu2+—L system at a micellar concentration promotes the formation of a dinuclear complex.

Thermodynamic stability of mercury(II) complexes formed with environmentally relevant low-molecular-mass thiols studied by competing ligand exchange and density functional theory

Environmental contextThe chemical speciation of mercury (Hg) largely controls its biogeochemical cycling and exposure to biota. Here, we investigate the thermodynamic stabilities of complexes formed between inorganic divalent Hg (HgII) and 15 biogeochemically relevant low-molecular-mass (LMM) thiol ligands. This information is critical for accurate modelling of the chemical speciation of HgII and to clarify the role of HgII–LMM thiol complexes in the cycling of Hg in the environment. AbstractInorganic divalent mercury (HgII) has a very high affinity for reduced sulfur functional groups. Reports from laboratory experiments suggest that HgII complexes with specific low-molecular-mass (LMM) thiol (RSH) ligands control rates of HgII transformation reactions. Because of methodological limitations for precise determination of the highly stable HgII complexes with LMM thiol ligands, constants reported in the literature remain inconsistent. This uncertainty impedes accurate modelling of the chemical speciation of HgII and the possibility to elucidate the role of HgII complexes with LMM thiols for Hg transformation reactions. Here, we report values of thermodynamic stability constants for 15 monodentate, two-coordinated HgII complexes, Hg(SR)2, formed with biogeochemically relevant LMM thiol ligands. The constants were determined by a two-step ligand-exchange procedure where the specific Hg(SR)2 complexes were quantified by liquid chromatography–inductively coupled plasma mass spectrometry. Thermodynamic stability constants (log β2) determined for the Hg(SR)2 complexes ranged from 34.6, N-cysteinylglycine, to 42.1, 3-mercaptopropionic acid, for the general reaction Hg2++2RS– ⇌ Hg(SR)2. Density functional theory (DFT) calculations showed that electron-donating carboxyl and carbonyl groups have a stabilising effect on the HgII–LMM thiol complexes, whereas electron-withdrawing protonated primary amino groups have a destabilising effect. Experimental results and DFT calculations demonstrated that the presence of such functional groups in the vicinity of the RSH group caused significant differences in the stability of Hg(SR)2 complexes. These differences are expected to be important for the chemical speciation of HgII and its transformation reactions in environments where a multitude of LMM thiol compounds are present.

Thermodynamic insight into solvent-effect on structures and antifungal activities of manganese(II) complexes with acylhydrazone

Three manganese(II) complexes, [Mn(HL)(EtOH)2Cl]2 (1), [Mn2(HL)2(EtOH)3(H2O)Cl2]2·[Mn(HL)(EtOH)(H2O)Cl]2·[Mn(HL)(EtOH)2Cl]2·4EtOH (2) and Mn(HL)2·2H2O (3) (H2L=N-(2-propionic acid)-(4-methoxy benzoyl) hydrazone), have been synthesized by self-assembly of MnCl2 with H2L in different ethanol/water systems. To better understand the thermodynamic stability of complexes with diverse structures, theoretical investigation of the electronic structures of the compounds has been carried out using density function theoretical calculations. Isothermal titration calorimetry (ITC) was employed to monitor the interactions between Mn(II) and H2L in different solvents, in which the binding constants (Ka) of the systems are 3.54×104, 3.66×104 and 34.97×104Lmol−1 for 1, 2 and 3, respectively. The thermodynamic calculation results indicate that the self-assembly of 1 and 2 are entropy-dominated spontaneous processes, while that of 3 is an enthalpy-driven one. In addition, solvent-effect on antifungal activity for compounds 1–3 was investigated.

Complexing properties of 1-[5-(hydrazidomethylsulfinyl)pentyl]-3,5-dimethylisocyanurate with cobalt(ii), nickel(ii), and iron(iii)

Composition and thermodynamic stability of complexes of 1-[5-(hydrazidomethylsulfinyl)pentyl]-3,5-dimethylisocyanurate with cobalt(ii), nickel(ii), and iron(iii) in H2O—DMSO medium (60 vol.% DMSO) was studied by spectrophotometry, potentiometric titration, and mathematical modeling (CPESSP program). The geometries of all studied structures were optimized by the MM2 molecular mechanics method to obtain the primary target data (estimates) on coordination pattern of 1-[5-(hydrazidomethylsulfinyl)pentyl]-3,5-dimethylisocyanurate in complexes with cobalt(ii), nickel(ii), and iron(iii). Cobalt(ii) and nickel(ii) formed the 1 : 1 complexes; while iron(iii) under experimental conditions excluding redox reactions gave the 1 : 1 and 1 : 2 complexes. All complexes contain ligands in neutral form.

Theoretical studies of complexes between Hg(II) ions andl-cysteinate amino acids

In this study, ab initio and density functional theory methods have been used to understand the structures and thermodynamic stabilities of complexes formed between l-cysteine and mercury (II) ions in neutral aqueous solution. To better understand the interaction between sulfur and mercury (II) ion, the MP2, B3LYP, M06-2X, and TPSS methods have been used to optimize [HgSHx]2−x, x = 1–4, complexes and compared to benchmark QCISD(T) structures. Furthermore, energies from these same methods are compared to CCSD(T)/CBS(2,3) energies. From these benchmark calculations, the M06-2X method was selected to optimize l-cysteinate-Hg(II) complexes and the MP2 method for estimating complex energies. l-cysteinate-mercury (II) ion complexes are formed primarily by forming a bond between cysteinate sulfur and the mercury ion. Stable complexes of l-cysteinate and mercury can be formed in 1:1, 2:1, 3:1, and 4:1 ratios. Each complex is stabilized further by interaction between carboxylate oxygen and mercury as well as hydrogen bonding among complex cysteinate ligands. The results indicate that at high cysteinate to Hg(II) ratios high-coordinate complexes can be present but at lower ratios the 2:1 complex should be dominant. © 2013 Wiley Periodicals, Inc.

Solution thermodynamic stability of complexes formed with the octadentate hydroxypyridinonate ligand 3,4,3-LI(1,2-HOPO): a critical feature for efficient chelation of lanthanide(IV) and actinide(IV) ions.

The solution thermodynamics of water-soluble complexes formed between Ce(III), Ce(IV), Th(IV) and the octadentate chelating agent 3,4,3-LI(1,2-HOPO) were investigated. Several techniques including spectrofluorimetric and automated spectrophotometric titrations were used to overcome the slow spontaneous oxidation of Ce(III) complexes yielding to stability constants of log β110 = 17.4 ± 0.5, log β11-1 = 8.3 ± 0.4 and log β111 = 21.2 ± 0.4 for [Ce(III)(3,4,3-LI(1,2-HOPO))](-), [Ce(III)(3,4,3-LI(1,2-HOPO)(OH)](2-), and [Ce(III)(3,4,3-LI(1,2-HOPO)H], respectively. Using the spectral properties of the hydroxypyridinonate chelator in ligand competition titrations against nitrilotriacetic acid, the stability constant log β110 = 41.5 ± 0.5 was determined for [Ce(IV)(3,4,3-LI(1,2-HOPO))]. Finally, the extraordinarily stable complex [Ce(IV)(3,4,3-LI(1,2-HOPO))] was used in Th(IV) competition titrations, resulting in a stability constant of log β110 = 40.1 ± 0.5 for [Th(IV)3,4,3-LI(1,2-HOPO))]. These experimental values are in excellent agreement with previous estimates, they are discussed with respect to the ionic radius and oxidation state of each cationic metal, and allow predictions on the stability of other actinide complexes including [U(IV)(3,4,3-LI(1,2-HOPO))], [Np(IV)(3,4,3-LI(1,2-HOPO))], and [Pu(IV)(3,4,3-LI(1,2-HOPO))]. Comparisons with the standard ligand diethylenetriamine pentaacetic acid (DTPA) provide a thermodynamic basis for the observed significantly higher efficacy of 3,4,3-LI(1,2-HOPO) as an in vivo actinide decorporation agent.

The speciation of lead in seawater by pseudopolarography using a vibrating silver amalgam microwire electrode

A novel electrode based on a vibrating silver amalgam microwire was used for pseudopolarography of lead (Pb) in seawater. Pseudopolarography is a method to study the stability of metal species by examination of their reduction potential. The reduction potential of kinetically irreversible species is related to the thermodynamic complex stability constant, whilst for labile species it is related to the conditional stability constant. The new electrode enables the speciation of Pb at picomolar level in uncontaminated seawater. The potential shift of electrochemically irreversible lead complexes was calibrated against the complex stability of several ligands in pH8 seawater. The method was compared against the mercury drop electrode at various concentrations of lead and various deposition times, and the response was in general agreement with the theory. The method is tested on samples from oceanic (Atlantic), coastal (Irish Sea) and estuarine (Mersey) origins at Pb concentrations between 30pM and 2nM. The pseudopolarograms were found to resolve the speciation of lead in terms of labile and irreversibly bound Pb species. The lead in the samples was largely in the labile component of the pseudopolarograms, indicating that it was reversibly complexed with values for log α′Pb2+L of 2 for the oceanic sample, and of 4 for the coastal sample. A smaller fraction was resolved as stable, irreversibly bound species with values for the thermodynamic stability constant of log KPb2+L=15–16. The speciation method was able to resolve metal species occurring at levels of only a fraction of that of the metal. Unlike copper, where organic complexation is strong and electrochemically irreversible, and able to significantly decrease its bioavailability, the Pb mostly occurs in the labile complexed fraction and is therefore readily available for geochemical scavenging or biological uptake reactions.

Selectivity of the Highly Preorganized Tetradentate Ligand 2,9-Di(pyrid-2-yl)-1,10-phenanthroline for Metal Ions in Aqueous Solution, Including Lanthanide(III) Ions and the Uranyl(VI) Cation

Some metal ion complexing properties of DPP (2,9-Di(pyrid-2-yl)-1,10-phenanthroline) are reported with a variety of Ln(III) (Lanthanide(III)) ions and alkali earth metal ions, as well as the uranyl(VI) cation. The intense π-π* transitions in the absorption spectra of aqueous solutions of 10(-5) M DPP were monitored as a function of pH and metal ion concentration to determine formation constants of the alkali-earth metal ions and Ln(III) (Ln = lanthanide) ions. It was found that log K(1)(DPP) for the Ln(III) ions has a peak at Ln(III) = Sm(III) in a plot of log K(1) versus 1/r(+) (r(+) = ionic radius for 8-coordination). For Ln(III) ions larger than Sm(III), there is a steady rise in log K(1) from La(III) to Sm(III), while for Ln(III) ions smaller than Sm(III), log K(1) decreases slightly to the smallest Ln(III) ion, Lu(III). This pattern of variation of log K(1) with varying size of Ln(III) ion was analyzed using MM (molecular mechanics) and DFT (density functional theory) calculations. Values of strain energy (∑U) were calculated for the [Ln(DPP)(H(2)O)(5)](3+) and [Ln(qpy)(H(2)O)(5)](3+) (qpy = quaterpyrdine) complexes of all the Ln(III) ions. The ideal M-N bond lengths used for the Ln(III) ions were the average of those found in the CSD (Cambridge Structural Database) for the complexes of each of the Ln(III) ions with polypyridyl ligands. Similarly, the ideal M-O bond lengths were those for complexes of the Ln(III) ions with coordinated aqua ligands in the CSD. The MM calculations suggested that in a plot of ∑U versus ideal M-N length, a minimum in ∑U occurred at Pm(III), adjacent in the series to Sm(III). The significance of this result is that (1) MM calculations suggest that a similar metal ion size preference will occur for all polypyridyl-type ligands, including those containing triazine groups, that are being developed as solvent extractants in the separation of Am(III) and Ln(III) ions in the treatment of nuclear waste, and (2) Am(III) is very close in M-N bond lengths to Pm(III), so that an important aspect of the selectivity of polypyridyl type ligands for Am(III) will depend on the above metal ion size-based selectivity. The selectivity patterns of DPP with the alkali-earth metal ions shows a similar preference for Ca(II), which has the most appropriate M-N lengths. The structures of DPP complexes of Zn(II) and Bi(III), as representative of a small and of a large metal ion respectively, are reported. [Zn(DPP)(2)](ClO(4))(2) (triclinic, P1, R = 0.0507) has a six-coordinate Zn(II), with each of the two DPP ligands having one noncoordinated pyridyl group appearing to be π-stacked on the central aromatic ring of the other DPP ligand. [Bi(DPP)(H(2)O)(2)(ClO(4))(2)](ClO(4)) (triclinic, P1, R = 0.0709) has an eight-coordinate Bi, with the coordination sphere composed of the four N donors of the DPP ligand, two coordinated water molecules, and the O donors of two unidentate perchlorates. As is usually the case with Bi(III), there is a gap in the coordination sphere that appears to be the position of a lone pair of electrons on the other side of the Bi from the DPP ligand. The Bi-L bonds become relatively longer as one moves from the side of the Bi containg the DPP to the side where the lone pair is thought to be situated. A DFT analysis of [Ln(tpy)(H(2)O)(n)](3+) and [Ln(DPP)(H(2)O)(5)](3+) complexes is reported. The structures predicted by DFT are shown to match very well with the literature crystal structures for the [Ln(tpy)(H(2)O)(n)](3+) with Ln = La and n = 6, and Ln = Lu with n = 5. This then gives one confidence that the structures for the DPP complexes generated by DFT are accurate. The structures generated by DFT for the [Ln(DPP)(H(2)O)(5)](3+) complexes are shown to agree very well with those generated by MM, giving one confidence in the accuracy of the latter. An analysis of the DFT and MM structures shows the decreasing O--O nonbonded distances as one progresses from La to Lu, with these distances being much less than the sum of the van der Waals radii for the smaller Ln(III) ions. The effect that such short O--O nonbonded distances has on thermodynamic complex stability and coordination number is then discussed.

Do Nonbonded H--H Interactions in Phenanthrene Stabilize It Relative to Anthracene? A Possible Resolution to this Question and Its Implications for Ligands such as 2,2′-Bipyridyl

The problem of whether interactions between the hydrogen atoms at the 1,10-positions in the "cleft" of the "bent" phenanthrene stabilize the latter molecule thermodynamically relative to "linear" anthracene, or whether the higher stability of phenanthrene is due to a more energetically favorable π-system, is considered. DFT calculations at the X3LYP/cc-pVTZ(-f)++ level of the ground state energies (E) of anthracene, phenanthrene, and the set of five benzoquinolines are reported. In the gas phase, "bent" phenanthrene was computed to be thermodynamically more stable than "linear" anthracene by -28.5 kJ mol(-1). This fact was attributed predominantly to the phenomenon of higher aromatic stabilization of the π-system of phenanthrene relative to anthracene, and not to the stabilizing influence of the nonbonding H--H interactions in its cleft. In fact, these interactions in phenanthrene were shown to be destabilizing. Similar calculations for five benzoquinolines (bzq) indicate that ΔE values vary as: 6,7-bzq (linear) ≤ 2,3-bzq (linear) < 5,6-bzq (bent) ≤ 3,4-bzq (bent) < 7,8-bzq (bent, no H--H nonbonding interactions in cleft), supporting the idea that it is a more stable π-system that favors 7,8-bzq over 2,3-bzq and 6,7-bzq, and that the H--H interactions in the clefts of 3,4-bzq and 5,6-bzq are destabilizing. Intramolecular hydrogen bonding in the cleft of 7,8-bzq plays a secondary role in its stabilization relative 6,7-bzq. The question of whether H--H nonbonded interactions between H atoms at the 3 and 3' positions of 2,2'-bipyridyl (bpy) coordinated to metal ions are stabilizing or destabilizing is then considered. The energy of bpy is scanned as a function of N-C-C-N torsion angle (χ) in the gas-phase, and it is found that the trans form is 32.8 kJ mol(-1) more stable than the cis conformer. A relaxed coordinate scan of energy of bpy in aqueous solution as a function of χ is modeled using the PBF approach, and it is found that the trans conformer is still more stable than the cis, but now only by 5.34 kJ mol(-1). The effect that the latter energy has on the thermodynamic stability of complexes of metal ions with bpy in aqueous solution is discussed.

Thermodynamic properties of donor–acceptor complexes of tertiary amine with aryl ketones in hexane medium

The thermodynamic stability of complexes formed between N,N-dimethylaniline (DMANI) and three ketones, namely, acetophenone (ACP), 4-chloroactophenone (ClACP) and 4-methylacetophenone (MACP) in n-hexane is extensively investigated by spectral and ultrasonic methods. The ultrasound scan was carried out in the temperature range 208.15–313.15 K and at atmospheric pressure on solutions containing equimolar concentrations of components ranging from 0.025 to 0.2 M. The existence of solute–solute interactions has also been confirmed through electronic absorption spectra analyzed with Benesi - Hildebrand theory at 303.15 K. The stability constants of the donor–acceptor complexes determined both by spectroscopic and ultrasonic methods are comparable and follow similar trends. The trend in the formation constants is discussed with structures of the components. The thermodynamic behavior of the systems was explained through the computed values of the free energy (Δ G ), enthalpy (Δ H ) and entropy (Δ S ) changes for complex formation are computed and discussed.

Equivalence of Mg 2+ and Na + ions in salt dependence of the equilibrium binding and dissociation rate constants of Escherichia coli RNA polymerase open complex

Conflicting experimental data on the influence of Mg 2+ ions on the salt dependence of formation/dissociation of open transcription complex (RPo) of Escherichia coli RNA polymerase led us to carry systematic measurements of the dissociation rate constant ( k d) and thermodynamic stability of complexes at λP R and Pa promoters in a broad range of [NaCl] and [MgCl 2] at 25, 31 and 37 °C, using fluorescence detected abortive transcription assay. Values of k d determined in MgCl 2 in the presence of heparin, as a commonly used anionic competitor, were shown to depend on heparin concentration whereas in NaCl this effect was not observed. Kinetics of dissociation was therefore determined in the course of salt-induced down-shift of the binding equilibrium. Salt derivatives of k d's ( n d) appeared to be similar in NaCl (~ 8.5) and MgCl 2 (~ 10) for both complexes. Isotherms of fractional occupancy of promoters by RNAP as a function of ln [salt] were shown to conform to a sigmoid Boltzman function parameterized to include binding constant of RPo and a net change ( n obs) in the number of electrolyte ions associated with complex components upon its formation/dissociation. The fitted values of n obs appeared also similar in NaCl and in MgCl 2: ~ 18 for RPo/λP R and ~ 20 for RPo/Pa, respectively. Overall unfavorable vant'Hoff enthalpy (Δ H obs) of RPo proved to be much higher in MgCl 2 than in NaCl by ca. 20 kcal/mol for both complexes, rendering them profoundly less stable in the former salt. In both salts, Δ H obs was higher by ~ 30 kcal/mol for RPo/Pa relative to RPo/λP R. Similarity of n obs and n d values for the two salts indicates thermodynamic equivalence of Mg 2+ and Na + in [salt]-controlled binding equilibrium of RPo. This finding remains in disagreement with earlier data and suggests that salt effects on open complex stability should be sought in global compensating changes in distribution of all ionic species around the interacting complex components.

1-Pyridine- and 1-Quinuclidine-1-boraadamantane as Models for Derivatives of 1-Borabicyclo[2.2.2]octane. Experimental and Theoretical Evaluation of the B−N Fragment as a Polar Isosteric Substitution for the C−C Group in Liquid Crystal Compounds

The suitability of 1-borabicyclo[2.2.2]octane (1) as a structural element for liquid crystals was evaluated using computational methods and experimental studies of two complexes of its close analogue 1-boraadamantane (2). The molecular and crystal structures for 1-pyridine-1-boraadamantane [2-P, C(14)H(20)BN, P2(1)/m, a = 8.4404(13) A, b = 6.8469(10) A, c = 10.5269(16) A, beta = 104.712(3) degrees, Z = 2], 1-quinuclidine-1-boraadamantane [2-Q, C(16)H(28)BN, P2(1)/n, a = 6.6529(3) A, b = 10.6665(6) A, c = 19.3817(10) A, beta = 94.689(3) degrees, Z = 4], and 1-pyridine-trimethylborane [3-P, C(8)H(14)BN, C(cma), a = 6.9875(10) A, b = 15.011(2) A, c = 16.556(2) A, Z = 8] were determined by X-ray crystallography and compared with the results of DFT and MP2 calculations. Gas-phase thermodynamic stabilities of complexes 1-P, 1-Q, 2-P, and 2-Q were estimated using a correlation between theoretical (MP2/6-31+G(d)//MP2/6-31G(d) with B3LYP/6-31G(p) thermodynamic corrections) and experimental data for complexes of BMe(3) (3) with amines lacking N-H bonds. The analysis showed the generally higher thermodynamic stability for the quinuclidine (Q) complexes compared to that of the pyridine (P) analogues in the gas phase and an overall order of stability of 1 > 2 > 3. This order is paralleled by high ring strain energy of 1 (SE = 27 kcal/mol) as compared to that of 1-boraadamantane (2, SE = 16.5 kcal/mol). The chemical stability of 2-P and 2-Q, with respect to hydrolytic and oxidative reagents, is high for the pyridine derivative and satisfactory for the quinuclidine complex at ambient temperature, which implies sufficiently high stability of 1-borabicyclo[2.2.2]octane complexes for materials applications. Molecular dipole moments of 6.2 +/- 0.1 and 6.0 +/- 0.15 D were measured for 2-Q and 2-P, respectively.

Complexation behaviour of (3,4-dihydroxyphenyl)alanine in some mixed coordinated systems : Equilibrium studies

Thermodynamic stability of complexes of Ni II and Co II with (3,4-dihydroxyphenyl)alanine (DOPA) and L-alanine, L-phenylalanine, L -aspartic acid and L-glutamic acid were investigated. Thermodynamic formation constants of these complexes were determined at three different ionic strengths at 20 ± 1°C and 30 ± 1 °C in aqueous medium under equimolar condition by subjecting experimental data to the computation applying SCOGS computer program. Thermodynamic parameters for mixed coordinated systems were calculated by using van't Hoff isotherm, van't Hoff isochore and Gibb's Helmholtz equation. Species distribution is obtained for all ternary (biligand) systems. Complexation behaviour of ligands is discussed.

Dynamics in Host–Guest Complexes of Molecular Tweezers and Clips

The dynamics in the host-guest complexes of the molecular tweezers 1 a,b and clips 2 a,b with 1,2,4,5-tetracyanobenzene (TCNB, 3) and tropylium tetrafluoroborate (4) as guest molecules were analyzed by temperature-dependent 1H NMR spectroscopy. The TCNB complexes of tweezers 1 a,b were found to be particularly stable (dissociation barrier: DeltaG(++)=16.8 and 15.7 kcal mol(-1), respectively), more stable than the TCNB complexes of clips 2 a,b and the tropylium complex of tweezer 1 b (dissociation barrier: DeltaG(++)=12.4, 11.2, and 12.3 kcal mol(-1), respectively). A detailed analysis of the kinetic and thermodynamic data (especially the negative entropies of activation found for complex dissociation) suggests that in the transition state of dissociation the guest molecule is still clipped between the aromatic tips of the host molecule. The 1H NMR analysis of the TCNB complexes 3@1 b and 3@2 a at low temperatures (T<-80 degrees C) showed that 3 undergoes fast rotation inside the cavity of tweezer 1 b or clip 2 a (rotational barrier: DeltaG( not equal)=11.7 and 8.3 kcal mol(-1), respectively). This rotation of a guest molecule inside the host cavity can be considered to be the dynamic equilibration of noncovalent conformers. In the case of clip complex 3@2 a the association and rotational barriers are smaller by DeltaDeltaG(++)=3-4 kcal mol(-1) than those in tweezer complexes 3@1 a,b. This can be explained by the more open topology of the trimethylene-bridged clips compared to the tetramethylene-bridged tweezers. Finally, the bromo substituents in the newly prepared clip 2 b have a substantial effect on the kinetics and thermodynamics of complex formation. Clip 2 b forms weaker complexes with (TCNB, 3) and tetracyanoquinodimethane (TCNQ, 12) and a more stable complex with 2,4,7-trinitrofluoren-9-ylidene (TNF, 13) than the parent clip 2 a. These results can be explained by a less negative electrostatic potential surface (EPS) inside the cavity and a larger van der Waals contact surface of 2 b compared to 2 a. In the case of the highly electron-deficient guest molecules TCNB and TCNQ the attractive electrostatic interaction is predominant and hence responsible for the thermodynamic complex stability, whereas in the case of TNF with its extended pi system, dispersion forces are more important for host-guest binding.

Novel macrocyclic EuII complexes: fast water exchange related to an extreme M-O water distance.

Eu(II) complexes are potential candidates for pO(2)-responsive contrast agents in magnetic resonance imaging. In this regard, we have characterized two novel macrocyclic Eu(II) chelates, [Eu(II)(DOTA)(H(2)O)](2-) and [Eu(II)(TETA)](2-) (H(4)DOTA=1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid, H(4)TETA=1,4,8,11-tetraazacyclotetradecane-1,4,8,11-tetraacetic acid) in terms of redox and thermodynamic complex stability, proton relaxivity, water exchange, rotation and electron spin relaxation. Additionally, solid-state structures were determined for the Sr(II) analogues. They revealed no inner-sphere water in the TETA and one inner-sphere water molecule in the DOTA complex. This hydration pattern is retained in solution, as the (17)O chemical shifts and (1)H relaxation rates proved for the corresponding Eu(II) compounds. The thermodynamic complex stability, determined from the formal redox potential and by pH potentiometry, of [Eu(II)(DOTA)(H(2)O)](2-) (lg K(Eu(II))=16.75) is the highest among all known Eu(II) complexes, whereas the redox stabilities of both [Eu(II)(DOTA)(H(2)O)](2-) and [Eu(II)(TETA)](2-) are inferior to that of 18-membered macrocyclic Eu(II) chelates. Variable-temperature (17)O NMR, NMRD and EPR studies yielded the rates of water exchange, rotation and electron spin relaxation. Water exchange on [Eu(II)(DOTA)(H(2)O)](2-) is remarkably fast (k298(ex)=2.5 x 10(9) s(-1)). The near zero activation volume (DeltaV++ =+0.1+/-1.0 cm(3) mol(-1)), determined by variable-pressure (17)O NMR spectroscopy, points to an interchange mechanism. The fast water exchange can be related to the low charge density on Eu(II), to an unexpectedly long M-O(water) distance (2.85 A) and to the consequent interchange mechanism. Electron spin relaxation is considerably slower on [Eu(II)(DOTA)(H(2)O)](2-) than on the linear [Eu(II)(DTPA)(H(2)O)](3-) (H(5)DTPA=diethylenetriaminepentaacetic acid), and this difference is responsible for its 25 percent higher proton relaxivity (r(1)=4.32 mM(-1) s(-1) for [Eu(II)(DOTA)(H(2)O)](2-) versus 3.49 mM(-1) s(-1) for [Eu(II)(DTPA)(H(2)O)](3-); 20 MHz, 298 K).