Capillary electrophoresis in N,N-dimethylformamide

N,N-Dimethylformamide (DMF) is a dipolar protophilic solvent with physicochemical properties that makes it suitable as solvent for capillary electrophoresis (CE). It is prerequisite for the proper application of CE to adjust and to change the pH of the background electrolyte (BGE) in a defined manner. This was done in the present work using benzoic acid-benzoate by selecting different concentration ratios of acid and salt, and calculating the theoretical pH from the activity-corrected Henderson-Hasselbalch equation. The mobilities of the analytes (chloro- and nitro-substituted phenolates) were found to follow reasonably well the typical sigmoid mobility versus pH curve as predicted by theory. The actual mobilities and pK(a) values (at 25 degrees C) of the analytes were derived from these curves. pK(a) values were in the range of 11.1-11.7, being thus 3-4.4 units higher than in water. This pK(a) shift is caused by the destabilization of the analyte anion and the better stability (solubility) of the molecular analyte acid in DMF, which overcome the higher basicity of DMF compared to water. Absolute mobilities were calculated from the actual mobilities; they were between 32x10(-9) and 42x10(-9) m(2)/Vxs. Slight deviations of the measured mobilities from the theoretical mobility versus pH curve were discussed on the bases of ion pairing and heteroconjugation and homoconjugation of either buffer components or buffer components and analytes. Heteroconjugation was used as a mechanism for the electrically driven separation of neutral analyte molecules in a BGE where salicylate acted as complex forming ion. Rough estimation of the complexation constants for the phenolic analytes gave values in the range of 100-200 L/mol. Addition of water to the solvent decreased the effect of heteroconjugation, but it was still present up to the surprisingly high concentration of 20% water. Electrophoretically relevant parameters like ionic mobilities and pK(a) values, and conjugation and ion pairing are dependent on the water content of the solvent. The water uptake of DMF was measured when exposed to humidity of ambient air. The resulted behavior of the water uptake was found rather similar to that for acetonitrile and methanol.     

Retention of ionizable compounds on HPLC. Modelling retention for neutral and ionizable compounds by linear solvation energy relationships

Summary A global LSER model that relates HPLC retention to mobile phase composition and pH is tested for a varied group of solutes, both neutral and ionizable, in a polymeric column and methanol-water mobile phases. It is compared to the local LSER model developed only for a given mobile phase, i.e., a fixed organic modifier content, and to the global LSER model set only for neutral solutes. The global LSER model for neutral and ionizable solutes requires a few supplementary parameters over the other models tested, but it accounts for retention under any experimental conditions for a given column and methanol-water mobile phases, describing properly the interactions established in the HPLC system (hydrophobicity, hydrogen-bond acidity and basicity, dipolarity/polarizability…). This paper is number 13 of a series with the same general title: “Retention of Ionizable Compounds on HPLC” published in various journals.     

Crystallization-driven self-assembly of isotactic polystyrene in N,N-dimethylformamide

Herein we demonstrate crystallization-driven self-assembly of isotactic polystyrene(i PS) with high isotacticity and narrow molecular weight distribution and crystallization-induced switching of the morphology of i PS aggregates in N, N-dimethylformamide(DMF). The formation and morphology switching of the self-assembled aggregates of i PS are investigated by means of dynamic light scattering(DLS), scanning electron microscopy(SEM), differential scanning calorimetry(DSC) and wide angle X-ray diffraction(WXRD). The results reveal that cooling DMF solution of i PS promotes i PS chains to self-assemble into spherical aggregates with a gelled core cross-linked by microcrystals, which is surrounded by solvent-swollen corona. Furthermore, crystallization induces the deformation of i PS aggregates from spherical to plate-like or nest-like.     

A theoretical study of the interactions between N,N-dimethylformamide and xylenes

The ab initio and density functional (DFT) methods were performed on binary systems of N,N-dimethylformamide (DMF) with xylenes (o-, or m-, or p-xylene), and seven stable configurations were obtained with no imaginary frequencies. To obtain the interaction energies of these complexes, single-point energy calculations with basis set superposition error (BSSE) correction were carried out at B3LYP/6-31G* and MP2/6-31G* levels. The structures, Chelpg (charges from electrostatic potentials using a grid-based method) charge distribution and bond characteristics of the mentioned complexes were calculated. The results indicated the presence of double C–H···O hydrogen bonds between DMF and xylenes in these complexes and the interaction energies of hydrogen bonding between DMF and xylene systems decreased in the following sequence: DMF–o-xylene: a1 > DMF–m-xylene: b1 > DMF–p-xylene: c1.     

Thermodynamics of solution of proto- and mezoporphyrins in N,N-dimethylformamide

This paper describes the results of thermodynamic study of dissolution of proto- and mesoporphyrins in liquid N,N-dimethylformamide (DMF) at different temperatures. Enthalpies of solution and solubility of protoporphyrin dimethylester (PDE) and mesoporphyrin dimethylester (MDE) in DMF have been obtained from T = (298 to 318) K. Free energies, enthalpies, entropies and heat capacities of solution have been computed from the combination of enthalpic and solubility data via the Gibbs–Helmholtz equation. We have shown that for all blood porphyrins this approach reproduces both free energies of solution and solubility values for the physiological temperature range.     

A theoretical study of the interactions between N, N-dimethylformamide and aromatic hydrocarbons

The B3LYP and MP2 methods with 6-31G* basis set were used to predict the geometries of N, N-dimethylformamide (DMF) dimer and DMF–aromatic hydrocarbons interaction systems. A total of 10 conformers were obtained with no imaginary frequencies, respectively. The interaction energies of these binary mixtures have been obtained. The analyses of chelpg charge distribution and the atoms in molecules theory (AIM) were used to analyze the nature of the interaction. The results show the presence of hydrogen bonds between DMF and aromatic hydrocarbons. The interaction between DMF and benzonitrile is the strongest with the interaction energy of −21.58 kJ mol⁻¹ (BSSE corrected), and the intensity order of interactions is DMF–benzonitrile: d2 > DMF–DMF: a2 > DMF–toluene: c1 > DMF–benzene: b2.     

Solvation of Na+ in N,N-dimethylformamide + methanol solutions. A nuclear magnetic relaxation study using dynamic solvent isotope effects

Inter- and intramolecular nuclear magnetic quadrupole relaxation measurements have been used to study the system methanol (CH₃OH)+ N,N-dimethylformamide (DMF)+NaI at 25°C. The dynamic behavior of the solvent molecules was investigated, throughout the composition range of the binary mixtures, by means of ¹⁴ N relaxation of DMF and ² H of methanol-d ₁ (CH ₃ OD). The intermolecular relaxation of ²³ Na⁺ in pure DMF was used to obtain information about the symmetry of the solvent electric dipole arrangement in the solvation sphere of the ion. The investigation of preferential solvation around Na⁺ in the binary mixtures was carried out by means of ²³ Na⁺ relaxation measurements using, for the first time, both the CH ₃ OH/CD ₃ OD and the DMF/DMF-d ₇ dynamic isotope effect. The results show that, throughout the composition range, there is preferential solvation by DMF. Furthermore, the use of the isotope effects of both components allowed for the first time a basic check of the reliability of the method since we obtained two independent sets of data for the composition of the Na⁺ solvation shell in the mixtures. The consistency of the two separate data sets demonstrates that the application of the dynamic isotope effect represents a powerful tool in preferential solvation studies.     

Analysis of amides in the air by sampling with SPME and detection by GC-FID

This paper proposes a solid-phase microextraction (SPME) method for the passive sampling and determination of N,N-dimethylacetamide (DMA) and N,N-dimethylformamide (DMF) in air by capillary GC with flame ionization detection. The optimized conditions for SPME method were grab sampling, polydimethylsiloxane/divinylbenzene fiber, extraction for 90 min at 25 +/- 2 degrees C, desorption for 3 min at 220 degrees C, and relative humidity 45 +/- 2%. Under these conditions, the method presented good linearity (R = 0.996), repeatability (%RSD 2.79 and 9.85 for DMF and DMA, respectively), and detection limit (0.021 and 0.024 mg/m3 for DMF and DMA, respectively).     

Thermophysical contribution of N,N-dimethylformamide in the molecular interactions with other solvents

This review delineates on molecular interactions of N,N-dimethylformamide (DMF) with some solvents reported by various thermodynamic and thermophysical measurements. Several topics and examples of thermodynamic studies are depicted on the basis of the present author's experience focusing on the structural behavior for binary and ternary mixtures of DMF with different non-electrolytes. Valuable information on the behavior and factors governing of the liquid structure of the strongly associated solvents are also reviewed. A discussion is presented and deviations are interpreted in terms of size, shape, the position of ketone group, the chain length of alkanol and hydrogen bond effects in the liquid mixtures to explain about chemical and thermophysical behavior. Our goal in this review is to provide the structural and thermophysical contribution of the literature related to DMF with other solvents. Eventually, we reviewed what has been learned about the excess volumes and ultrasonic studies of ternary mixtures containing DMF with other solvents from experimental studies and also summarized the important contributions of DMF in the molecular interactions with other solvents.     

Screening of N,N‐bidentate and N,N,N‐tridentate pyridine‐based ligands in the catalytic allylic oxidation of cyclic olefins

A variety of chiral N,N‐bidentate and N,N,N‐tridentate ligands based on the pyridine framework, namely C2‐symmetric dipyridylmethane and terpyridine, N‐(p‐toluensulfinyl)iminopyridines and two kinds of iminopyridines, has been assessed in the asymmetric copper(I)‐catalysed allylic oxidation of cyclic olefins. Catalytic activity and enantioselectivity were found to be highly dependent upon the framework of the ligands, which afforded cycloalkenyl benzoates in low to moderate yields and enantioselectivities. The best yields (up to 70%) and enantioselectivities (up to 53% enantiomeric excess) were obtained with an iminopyridine based on camphane and quinoline skeletons. Copyright © 2014 John Wiley & Sons, Ltd.     

Conformational aspects of the solvation of polyhydroxy compounds in binary mixtures of N,N-dimethylformamide and water

Enthalpies of solution of -D-fructose and sucrose in binary solvent mixtures of water and N,N-dimethylformamide (DMF) at 25°C over the whole mole fraction region are reported and compared to those of -D-glucose. Because in these solvent systems the mutarotation of -D-fructose is fast and accompanied by large enthalpy changes, the measured enthalpies of solution of this compound had to be corrected for this effect. The dependences of the enthalpies of solution on the composition of the solvent mixtures are considered to result from preferential hydrogen-bonding of the hydroxyl groups and hydrophobic hydration of the apolar parts of the surface of the solute molecule. Distinctions between the enthalpy of transfer curves are discussed in terms of conformational differences and additivity aspects in the solvation behavior of the compounds. The predominance of furanose forms of fructose in DMF and that of pyranose forms of the same solute in water are related to differences in solvation.     

Structure and stability of hydrogen fluoride complexes with N,N-dimethylformamide

The structure, stability, and paths of formation of 11 (HF)_m(DMF)_n heterocomplexes (m = 1–4, n = 1, 2) were studied in terms of the B3LYP/6-31++G(d, p) density functional calculation. The results of this calculation suggest that: a) addition of hydrogen fluoride molecules to the (HF)_mDMF cyclic fragment is the basic tendency in complex formation in the HF-DMF system; b) data about the structure and properties of stable molecular forms that prevail in N,N-dimethylformamide solutions of hydrogen fluoride can be obtained by quantum chemical calculations for (HF)_mDMF complexes (m = 5–10).     

Dielectric relaxation studies of aqueous N,N-dimethylformamide using a picosecond time domain technique

The dielectric relaxation studies of N,N-dimethylformamide at thirteen concentration in aqueous solutions have been carried out using a time domain reflectometry technique in the frequency range 10 MHz to 10 GHz. The dielectric parameters and excess dielectric properties have also been determined from 5 to 40°C. The Luzar theory was applied to compute the cross correlation terms for the mixture. It adequately reproduces the experimental values of the static dielectric constants. The Bruggeman model for the nonlinear case has been fitted to the dielectric data for mixtures.     

Enthalpies of transfer of N-methylformamide,formamide, and N,N-dimethylformamide from methanol to methanol+dimethylsulfoxide mixtures

The enthalpies of transfer of formamide, N-methylformamide and N,N-dimethylformamide from methanol to methanol+dimethylsulfoxide solvent systems have been measured. These data are analysed in terms of a recently developed model of solvation in mixed solvents. The results of the data analyses indicate that preferential solvation of the different functional groups of the amides differs, the carbonyl oxygen being preferentially solvated by methanol and the nitrogen protons are by dimethylsulfoxide.     

Densities and excess molar volumes for binary mixtures of N,N-dimethylformamide+ 1,2-dimethoxyethane

Densities are reported for N,N-dimethylformamide and 1,2-dimethoxyethane binary mixtures at different mole fractions covering the whole miscibility range and at 19 temperatures ranging from –10 to 80°C. The experimental density data have been fitted by empirical relations and the excess volumes by a Redlich-Kister equation. The 11 N,N-dimethylformamide and 1,2-dimethoxyethane adduct appears to be stable throughout the temperature range. A comparison with other DMF containing mixtures is made.