Micellar-mediated shifts of ionization constants of amino acids and peptides

The acid-base dissociation constants, K_a, of amino acids and small peptides were determined in both aqueous and micellar solutions of sodium dodecyl sulfate and cetyltrimethylammonium bromide by potentiometric and chromatographic means. The observed differences in pK_a values between micellar media and aqueous solutions ranged between 0.23 and 2.21 units. The micellar-mediated pK_a shifts can be attributed to different solute-micelle interactions, mainly hydrophobic and electrostatic forces. The implications of the change in acid-base behavior on separation selectivity in micellar liquid chromatography and micellar electrokinetic capillary chromatography are discussed.     

Bi-ionic membrane potential across a liquid anion-exchange membrane containing triphenyltin chloride

Potentiometric selectivities of a liquid anion-exchange membrane containing triphenyltin chloride (TPTCl) to several inorganic anions were evaluated via measurements of the membrane potential of a bi-ionic system, also called bi-ionic membrane potential. Addition of TPTCl to the liquid anion-exchange membrane, based on the quaternary ammonium salt, gave rise to a quite different selectivity pattern from the so-called Hofmeister anion series observed for the liquid anion-exchange membrane. An additivity rule of the bi-ionic membrane potential was observed to hold for the liquid anion-exchange membrane containing TPTCl. Thus, the following multiple chain rule was derived for selectivity coefficients; k_1,n^pot = k_1,2^pot · k_2,3^pot … k_i,(i+1)^pot … k_n−1,n^pot where k_i,i+1^pot is the selectivity coefficient of the membrane for the (i + 1)th ion over the ith ion.     

Determination of pKa values of some hydroxylated benzoic acids in methanol-water binary mixtures by LC methodology and potentiometry

An accurate estimation of pK_a values in methanol-water binary mixtures is very important for several separation techniques such as liquid chromatography and capillary electrophoresis that use these solvent mixtures. In this study, the pK_a values of 11 polyphenolic acids have been determined in methanol-water binary mixtures (10%, 20% and 30% (v/v)) by potentiometry, liquid chromatography (LC) and LC-DAD methodology.The results show a similar trend for the pK_a values of all the studied compounds, as they increase with increasing concentration of organic modifier, which allows a linear relationship between pK_a values and mole fraction of methanol to be obtained. The pK_a values obtained in aqueous medium have been compared with those given in the literature, and also with the values predicted by the SPARC on-line pK_a calculator. The data obtained have been used to test the feasibility of an estimation of dissociation constants in a methanol-water medium from the relationship between pK_a values and the organic cosolvent fraction in the mixtures.     

Selective electrochemical molecular recognition of benzenediol isomers using molecularly imprinted TiO2 film electrodes

In this paper, selective recognition of benzenediol isomers was studied using molecularly imprinted TiO₂ film formed on a graphitic electrode. The imprinting process was investigated in detail using IR. The electrode process for p-hydroquinone follows a E_rC_r mechanism. The cavities formed by p-phthalic acid have good selectivity toward p-hydroquinone among the isomers. The complex ratio between p-hydroquinone and binding sites was estimated to be 1:2 with an apparent equilibrium constant of 2.98×10⁶ l² mol⁻². For o-hydroquinone and m-benzenediol, the ratio decreased to 1:1 with an apparent equilibrium constant of 1.20×10³ and 1.35×10³ l mol⁻¹. The apparent complexing ratio and equilibrium constants could shed some insight on the nature of isomeric selectivity of the recognition sites with respect to different isomers of benzenediol. The cavities designed by o-phthalic acid present good selectivity toward o-hydroquinone.     

Competition among aromatic guests for the host tetrakis(4-methylpyridine)nickel(II) isothiocyanate and a basis for the observed selectivity

In continuing attempts to determine the basis for the selectivity shown by the host Ni(4-mepy)₄(NCS)₂ (1) toward aromatic guests, distribution data between solid and liquid phases are reported for seven ternary systems at room temperature. These consist of1,p-xylene, and each of the following:p-bromotoluene,p-chlorotoluene,p-fluorotoluene,p-dichlorobenzene, benzene, and 4-methylpyridine, as well as the system1-p-chlorotoluene-p-dichlorobenzene. The results, as well as those for five systems already published, have been reviewed and a hierarchy of selectivity developed. After correcting the observed selectivity for inequality of guest vapour pressures the order of decreasing preference is found to bep-bromotoluene >p-dichlorobenzene >p-chlorotoluene > deuterated and protiatedp-xylenes > ethylbenzene > 4-methylpyridine >p-fluorotoluene > toluene > benzene. With the exception of 4-methylpyridine, this is the same as the order of decreasing van der Waals length of the guest molecule and, where known, the order of enthalpy of inclusion. Although longer guest molecules and those with higher vapour pressures are favoured in selectivity, guests with longer molecules are likely to have lower vapour pressures. The activity coefficients of the included guests are calculated assuming that the liquid phases follow Raoult's law.Portions of this paper were presented at the Second and Fourth International Symposia on Clathrate Compounds and Molecular Inclusion Phenomena held in Parma, Italy, 1982 and Lancaster, England, 1986.     

Enrichment and sensitive determination of dichlorodiphenyltrichloroethane and its metabolites with temperature controlled ionic liquid dispersive liquid phase microextraction prior to high performance liquid phase chromatography

Dichlorodiphenyltrichloroethane (DDT) and its main metabolites are important environmental pollutants and have been in the focusing center. It is of great value to develop simple, rapid, sensitive and easy to operate method for monitoring them. Present work established a novel temperature controlled ionic liquid dispersive liquid phase microextraction method in combination with high performance liquid chromatography for the enrichment and determination of DDT and its metabolites. Proposed method used only ionic liquid 1-hexyl-3-methylimidazolium hexafluorophosphate ([C₆MIM][PF₆]) for the enrichment and overcame the demerits of conventional single drop liquid phase microextraction and dispersive liquid-liquid microextraction. Temperature has two functions here, one is to promote the dispersing of ionic liquid into the solution and forming infinitesimal micro-drop and increasing the chance of the analytes extracted into ionic liquid phase, and the other one is to perform phase-separation. A series of factors that would affect the extraction performance was systematically investigated and optimized. The experimental results indicated that the detection limits obtained for p,p′-DDD, p,p′-DDT, o,p′-DDT and p,p′-DDE were 0.24, 0.24, 0.45, 0.24 ng mL⁻¹, respectively. The linear ranges for them were from 1.0 to 100 ng mL⁻¹, and the precisions were between 3.8% and 6.7% (n = 6). The proposed method was validated with four real-world samples and excellent results were achieved.     

Role of steric factors in the mechanism of separation of structural isomers with nematic sorbents

The model of a nematic binary mixture of rigid biaxial molecules is used to calculate the coefficients of selectivity enhancement S _m/p (the ratio between the activity coefficients ofmeta- andpara-substituted benzenes as sorbates at infinite dilution) in the nematogenic matrix of a nematic liquid-crystal sorbent and the parameters of orientation order of the components. It was found that in systems of particles in which interaction between the particles consists in steric repulsion, the Sm/p coefficient is less than 1 and is practically constant in the isotropic phase, whereas in the nematic phase, S _m/p is greater than 1 and increases in parallel with the order parameter.     

Selectivity of Several Liquid Phases for the Separation of Pine Terpenes by Gas Chromatography

Chromatographic retention data and thermodynamic properties of six pine terpenes (α-pinene, β-pinene, camphene, limonene, α-phellandrene and p-cymene) on six different liquid phases, with a wide range of polarity, are reported at temperatures from 80 to 120 °C. The retention behaviour and selectivity of liquid phases for the separation of binary solute systems are discussed in terms of activity coefficients and specific interactions. Solubility parameters for the liquid phases are reported using the regular solution theory and the Takamiya equation and a good correlation between polarity and solubility parameters is observed.     

Search for ultra slow molecular motion in liquid crystals by spin thermometry

The existence of a slow dynamic mode, which relaxes the nuclear Zeeman energy at low fields, has been detected in liquid crystals by several nuclear magnetic resonance studies. To data, through, this slow mode has not been uniquely determined. The cross relaxation in the liquid crystal PAA and the dimer-exchange in the alkoxy-benzoic acid homologous series, interfere with the analysis of the low frequency relaxation. In p-(pentyl) phenyl-p-pentyloxy benzoate, which is not a dimer and cross relaxation between protons and other nuclei is not possible, the spin relaxation was analysed at low and high fields. By measuring T₁, T_1ρ, T_1D and applying spin thermometry, the existence of a slow mode was uniquely determined in this liquid crystal.     

Selective separation of aromatic hydrocarbons through supported liquid membranes based on ionic liquids

Ionic liquids are emerging as alternative solvents for volatile organic compounds traditionally used in liquid–liquid extraction and liquid membrane separation. In this paper, we examine whether room-temperature ionic liquids as a membrane solution can be utilized for hydrocarbon separation by using a supported liquid membrane. Aromatic hydrocarbons, benzene, toluene and p-xylene were successfully transported through the membrane based on the ionic liquids. Although the permeation rates through the membrane based on the ionic liquids were less than those of water, the selectivity of aromatic hydrocarbons was greatly improved. The maximum selectivity to heptane was obtained using benzene in the aromatic permeation and 1-n-butyl-3-methylimidazolium hexafluorophosphate in the liquid membrane phase.     

Sorption and selective properties of binary liquid-crystalline sorbent based on 4-Methoxy-4′-ethoxyazoxybenzene and a cetylated β-Cyclodextrin

The mesomorphous, sorption, and selective properties of a binary sorbent based on achiral liquid crystal 4-methoxy-4′-ethoxyazoxybenzene and macrocyclic heptakis(2,3,6-tri-O-acetyl)-β-cyclodextrin (10.25 wt %) are investigated. Macrocyclic additive was found to induce the formation of a helically twisted nematic phase (N*). The standard and excess thermodynamic functions of sorption by binary sorbent from gaseous phase are determined for 29 organic compounds (n-alkanes, cycloalkanes, arenes, monoatomic alcohols, heterocycles, optical isomers of camphene, limonene, and butanediol-2,3). The investigated sorbent is found to have high structural selectivity over the wide temperature range of the N* mesophase (α _p/m = 1.11–1.06, 95–120°C) and moderately expressed enantioselectivity within the narrow region of transition from the solid crystalline state to the N* mesophase (α_+/? = 1.024–1.088, 91–100°C).     

Reaction between phenol and 130–190°C fraction of liquid pyrolysis products in the presence of catalyst KU-23 in a continuous plant

The results of the alkylation of phenol by 130–190°C fraction of the liquid pyrolysis products in the presence of a catalyst KU-23 of H-form carried out in a continuous plant were reported. Optimal conditions for the synthesis of p-alkyl phenol were found. It was shown that under the optimal mode a yield of target alkyl phenol was 69.7% of theory and selectivity, 93.3%. p-Alkyl phenolamine resin tested as an antioxidant engine oil at high temperatures was synthesized on the basis of p-alkyl phenol and hexamine.     

On the effect of the porosities of microporous membranes on their ionic selectivities

In order to help clarify the correlation between the structure and the transport parameters in the microporous membranes mentioned in this paper, the effect of porosity upon ionic selectivity is examined for Nucleopore®, Millipore® and Pall® membranes. These membranes separate two NaCl solutions of concentrations c₁ (constant for all the experiment,) and c₂ (fixed for each experiment, c₂ >c₁). The concentrations are small enough to take the place of the activities in the transport equations. The temperature is 298.0 ± 0.1 K and the stirring speed used to homogenize the solutions is 50 rpm.The ionic selectivity is characterized, in the steady state, by an experimental parameter K, which is obtained from measurements of the membrane potential as a function of the relative saline concentration n_c = c₂/c₁ (with c₁ being constant). This parameter K makes it possible to obtain the relative ionic permeability n_p = P_-/P₊ and the transport numbers. The relation between K, n_p and t₊ or t_- is obtained by integrating the Nernst-Planck equations and making use of the Goldman hypothesis of constant electric field. The porosity θ, expressed in percents of the empty volume over the total volume of the membrane, is measured by means of a pycnometric method which is explained in this paper. From the values of K and θ, obtained for the membranes and experimental conditions of these experiments, it can be concluded that ionic selectivity increases linearly with porosity.     

Vibrational relaxation of liquid benzene. A temperature-dependent Raman lineshape study of the selectively deuterated molecules

The halfwidths of the symmetric CH and CD stretching modes of liquid C₆H₆, C₆D₆, sym-C₆D₃H₃, p-C₆H₂D₄, p-C₆H₄D₂, C₆HD₅, and C₆H₅D are reported. Their temperature dependence is measured in nearly the whole liquid range. There is no coincidence with present relaxation theories.     

Comparison of thermal curing behavior of liquid and solid urea–formaldehyde resins with different formaldehyde/urea mole ratios

This study was undertaken to compare thermal cure kinetics of urea–formaldehyde (UF) resins, in both liquid and solid forms as a function of formaldehyde/urea (F/U) mole ratio, using multi-heating rate methods of differential scanning calorimetry. The requirement of peak temperature (T _p), heat of reaction (ΔH) and activation energy (E) for the cure of four F/U mole ratio UF resins (1.6, 1.4, 1.2 and 1.0) was investigated. Both types of UF resins showed a single T _p, which ranged from 75 to 118 °C for liquid resins, and from 240 to 275 °C for solid resins. As the F/U mole ratio decreased, T _p values increased for both liquid and solid resins. ΔH values of solid resins were much greater than those of liquid resins, indicating a greater energy requirement for the cure of solid resins. The ΔH value of liquid UF resins increased with decreasing in F/U mole ratio whereas it was opposite for solid resins, with much variation. The activation energy (E _a) values calculated by Kissinger method were greater for solid UF resins than for liquid resins. The activation energy (E _α ) values calculated by isoconversional method which showed that UF resins in liquid or solid state at F/U mole ratio of 1.6 followed a multi-step reaction in their cure kinetics. These results demonstrated that thermal curing behavior of solid UF resin differed greatly from that of liquid resins, because of a greater branched network structure in the former.     

Synthesis of rhodium N-heterocyclic carbene complexes and their catalytic activity in the hydrosilylation of alkenes in ionic liquid medium

Rhodium complexes bearing N-heterocyclic carbene (NHC) ligands were prepared from bis(η⁴-1,5-cyclooctadiene) dichlorodirhodium and 1-alkyl-3-methylimidazolium-2-carboxylate, and the catalytic properties of rhodium complexes prepared in the hydrosilylation of alkenes in ionic liquid media were investigated. It was found that both the catalytic activity and selectivity of the rhodium complexes bearing NHC ligands were influenced by the attached substituents of the imidazolium cation. Additionally, rhodium complexes bearing NHC ligands in ionic liquid BMimPF₆ could be reused without noticeable loss of catalytic activity and selectivity.     

A Novel Production of γ-Butyrolactone Catalyzed by Homogeneous Ruthenium Complexes

γ-Butyrolactone (hereafter abbreviated GBL) is produced by the two-stage hydrogenation of maleic anhydride(MAH) in the liquid phase: the hydrogenation of MAH to succinic anhydride(SAH) in the first stage and the subsequent hydrogenation of SAH to GBL in the second stage. A novel ruthenium catalyst system consisting of Ru salts, trialkylphosphine and p-toluene sulfonic acid (p-TsOH) was found very effective for the hydrogenation of SAH affording GBL, which exhibited excellent catalyst performance, exceeding 97% selectivity for GBL and high activity.     

1-Butyl-3-methylimidazolium p-toluenesulfinate: a novel reagent for synthesis of sulfones and β-ketosulfones in ionic liquid

A novel task-specific ionic liquid, 1-butyl-3-methylimidazolium p-toluenesulfinate, [bmim][p-TolSO₂] has been synthesized and used as a nucleophile for the reaction with alkyl bromides and phenacyl bromides to prepare sulfones and β-ketosulfones in excellent yields (80-93%) in [bmim][BF₄] ionic liquid. The isolated yields of sulfones and β-ketosulfones were higher in [bmim][BF₄] than other organic solvents at room temperature.     

Remote stereocontrol by the sulfinyl group. Diels–Alder reaction of cyclopentadiene with substituted (S)-[2-(p-tolylsulfinyl)styrenes and (S)-[2-(p-tolylsulfinyl)phenyl] vinyl ketones

The ability of a homochiral sulfinyl group at the dienophile to act as a remote stereocontrol inductor in the Diels–Alder reaction with cyclopentadiene has been evaluated. High pressure conditions were required for the reactions of (S)-2-(p-tolylsulfinyl)styrenes 3–5 (E-1,2-disubstituted double bond) and 6–8 (1,1-disubstituted double bond). A good facial selectivity and total endo selectivity were attained with 1,1-disubstitued dienophiles, though the 1,2-disubstituted ones afforded poorer results. In contrast, (S)-[2-(p-tolylsulfinyl)phenyl] vinyl ketones 9–11 reacted readily at low temperature (?40 °C) with complete endo selectivity and high facial selectivity in the presence of Yb(OTf)₃ as a chelating reagent of sulfinyl and carbonyl oxygen atoms. Concerning furan reactions, β-trifluoromethyl enone 14 afforded Diels–Alder adducts with high facial selectivity in the presence of the Lewis acid, but β-non-substituted enones 9 and 12 yielded products of furan conjugate addition to the double bond.