Optical purity, enantiomeric excess and the Horeau effect

Optical purity (op) and enantiomeric excess (ee) become equal when either heterochiral dimerization constant is twice that of homochiral dimerization constant or specific rotations of monomer and dimer are equal.

Self-Association of the Macromolecules of Aldrich Humic Acid in Aqueous Solutions Using Ultraviolet–Visible (UV–Vis) Absorption Spectroscopy

The ultraviolet–visible (UV–Vis) spectra of the aqueous solutions of humic acids (HA) Aldrich were obtained within the concentration range 1–20 mg/L (0.1–2ċ10–6 mol/L). A conclusion on the existence of the self-association (dimer formation) of HA macromolecules is based on the deviation of the concentration dependence of optical density (OD) from the linear one at [HA] > 10 mg/L (>10–6 mol/L). An original, mathematical algorithm is proposed to determine a dimerization constant K and a molar coefficient of dimer absorption [Formula: see text] The value of K was (2.56 ± 0.07) ċ 106 L/mol. The calculated molar coefficients of HA macromolecule dimer absorption, [Formula: see text], indicate an increase in the dimer extinction coefficient [Formula: see text] compared to the double value of the molar monomer absorption 2[Formula: see text]. It was established that the spectral dependence of the value β = [Formula: see text]/[Formula: see text] exhibits a minimum within a wavelength range of 300–450 nm, which is due to the difference in the efficiency of the interaction of various sites upon HA macromolecule dimerization. Thus, an approach of studying the processes of self-association is proposed using the method of UV–Vis absorption spectroscopy. This method is implemented for molecules that do not have characteristic absorption bands. The proposed method can also be successfully applied to molecules with characteristic absorption bands.

The Dimerization Effects of Some Solutes on the Partition Coefficient kD in Binary Immiscible Solvents

The dimerization of a solute dissolved in binary immiscible solvents shows that the value of the partition coefficient, kD of the solutes are influenced by the dimerization constant, K of the solute in one of the solvents according to the description: (C_X^A)/(C_X^B ) = kD + 2kD2KCxB where CxA and CxB are the concentrations of the solute x in the solvents A and B respectively. Both kD and K are parameters that predict the extent of beneficiation for most minerals. Also, kD is a fundamental parameter that determines the extent of solute recovery during solvent extraction. In this study, it is found that the order K kD and K kD are the effects for acetic and succinic acids respectively in the binary solvents composed of carbon tetrachloride/water and diethylether/water systems respectively. These results suggest that the distributions of these solutes in the solvents are accompanied by the formation of succinic anhydride which is more favoured than the dimerization of the acetic acid. Also, the changes in the values of distribution enthalpies, HD are corroborated to explain these experimental observations.

Study of the coordination of quinuclidine to a chiral zinc phthalocyanine dimer

We attempted the calculation of an accurate equilibrium constant for the dimerization process of enantiomerically pure Zn-1 using UV-vis dilution experiments. At millimolar concentration Zn-1 is involved in a chemical exchange process between its monomeric and dimeric state that is slow on the 1H NMR timescale. We performed variable-temperature 1H NMR experiments in CDCl3 solution to determine the dimerization constant value at different temperatures and performed a van’t Hoff plot to derive the thermodynamic parameters of the process. The calculated thermodynamic data revealed that the dimerization process is entropy-driven and enthalpically opposed. We also probed the coordination of quinuclidine, 1-azabicyclo[2.2.2]octane, 2, to the Zn-1 using UV-vis and 1H NMR titrations in CDCl3 solution. At micromolar concentration the Zn-1 exclusively exists in solution as a monomer and forms a simple 1:1, [Formula: see text], complex with quinuclidine having a stability constant of [Formula: see text]([Formula: see text]) [Formula: see text] 106 M[Formula: see text]. On the other hand, the 1H NMR titrations carried out at 298 K and at millimolar concentration showed that Zn-1 was present in solution as the dimer and formed 1:2, [Formula: see text], and 2:2, [Formula: see text] complexes by coordination to 2. In addition, the 1:1 complex, [Formula: see text] showed a reduced dimerization constant compared to the uncoordinated parent monomer Zn-1. At high quinuclidine concentration, the 1:1 complex, [Formula: see text], derived from the coordinated dimer dissociation was also detected. The 1H NMR spectra of the titrations displayed separate signals for some hydrogen atoms of the Zn-phthalocyanine in each one of the four species. Remarkably, the chemical exchange processes involving free and bound quinuclidine in the monomeric and dimeric complexes showed different kinetics on the NMR timescale.

Study on the Effect of an Electrolyte on the Self-Aggregation and the Geometry of the Dye Aggregates of Methylene Blue in Aqueous Media

The self-aggregation of Methylene Blue (MB) dye in aqueous media has been investigated spectrophotometrically in presence of sodium chloride (NaCl) at 293.15, 303.15 and 313.15K. The dimerization constant (K_D) of the MB dye in aqueous solution with or without the electrolyte has been computed using a non-linear least square regression technique. It is observed that presence of the electrolyte resulted into sharp increase in K_D of MB indicating that presence of the electrolyte favours formation of dye aggregates. There is, however, a decrease in K_D with increase in temperature. From the observed spectra of the dye, the twist (θ₁) and the tilt (θ₂) angles between the dipoles of MB molecules in the aggregates have been computed based on exciton model. Change in the monomeric fractions of the dye (α) in presence of the added electrolyte as a function of the dye concentration has also been computed. The results indicated that the dye aggregates formed is essentially of the sandwich type geometry (H-aggregates) with a slight deviation from an exact parallel stacking arrangement and reduced twist angle. The thermodynamic parameters of the aggregation process in presence of the electrolyte have been evaluated from the temperature dependence of K_D. It is observed that the aggregation process is an enthalpy rather than entropy controlled one.

Optimized synthesis of a tert-butyl-phenyl-substituted tetrapyridophenazine ligand and its Ru(ii) complexes and determination of dimerization behaviour of the complexes through supramolecular “Fingerhakel”

A high dimerization constant of a ruthenium complex is observed with the aid of 1H-NMR spectroscopy. The solid state molecular structure indicates that multiple π-interactions are the reason for strong dimerization.

The Investigation of the Neopluramycin � DNA System by UV-visible Spectroscopy

The self-association of neopluramycin and the binding of this drug to calf thymus DNA were investigated by using UV-visible spectroscopy. This classical pluramycin antibiotic self-associates in 1:1 ethanol - water mixture. Starting from a simple dimerization model, the molar absorption coefficient of monomer, the molar absorption coefficient of dimer and the dimerization constant were determined. The binding constant of neopluramycin to DNA was determined using Wolfe and Scatchard methods.