Monte Carlo simulation of 2-ethoxyethanol in continuum configurational biased procedure: conformational analysis and association in aqueous and non-aqueous media

 Monte Carlo simulations have been carried out for 2-ethoxyethanol (C₂E₁) in isothermal-isobaric ensemble (NPT) at different temperatures and 1 atm pressure with a continuum configurational biased procedure in water and chloroform media. Hydrogen bond bridges were formed between adjacent oxygen atoms in C₂E₁ (CH₃CH₂OCH₂CH₂OH) through water molecules. We also found that the stable conformers of C₂E₁ in water and CHCl₃ are different and the effect of temperature on solute-solvent interaction energies is considerable. The self-association of C₂E₁ in aqueous and nonaqueous media has been studied by statistical perturbation theory, and the relative free energy has been obtained at different reaction coordinates by double-wide sampling method. Two minima were found in water solvent in the potential of mean force (PMF), corresponding to the contact and solvent-separated pairs, but only one minimum was found in CHCl₃ solvent corresponding to a contact pair complex. Received: 18 January 2001 / Accepted: 22 October 2001 / Published online: 21 January 2002     

Thermodynamics of aqueous mixtures of 2-(2-Hexyloxyethoxy)ethanol at 5°C

The densities and the ultrasonic speeds of the aqueous solutions of 2-(2-hexyloxyethoxy)ethanol (C₆E₂) were measured over the entire range of mole fractions at 5°C. Excess molar volumes V ^E were readily calculated from the densities. The densities, in combination with the ultrasonic speeds, furnish estimates of the molar (and excess molar) isentropic compressibilities K _S and the deviations u ^D of the ultrasonic speeds from the values calculated for ideal mixtures. Radical changes in the mole fraction derivatives of the excess molar properties of the (C₆E₂ + water) system, in the vicinity of an amphiphile mole fraction of 0.003, indicate that C₆E₂ like C₆E₃ is capable of micelle formation. Our data have been compared with those reported earlier for (C₄E₂ +, C₂E₂ +, and C₆E₃ + water). We have employed both mass action and pseudophase approaches to data analysis, together with the four-segment model approach.     

Gas chromatographic analysis of C2−C16 dicarboxylic acids esterified in aqueous solutions as n-propyl esters

Summary C₂−C₁₆ dicarboxylic acids were esterified in aqueous solution in the presence of sulfuric acid. Esterification in water/n-propanol mixtures with mole ratios between 0.03 and 2.21 can be utilized for the quantitative determination of dicarboxylic acids by gas chromatography. The presence of water does not interfere at water/n-propanol mole ratios below 0.45. For mole ratios above 0.45 anhydrous sodium sulfate has been used for binding the water. The mole ratio range tested was 0.12–0.99 for anhydrous sodium sulfate/water, and 0.16–2.55 for sulfuric acid/anhydrous sodium sulfate.     

Micellization of sodium dodecyl sulfate and polyoxyethylene dodecyl ethers in solution

The effect of polyoxyethylene type nonionic surfactants (C₁₂E _n n = 3, 4, 5, 6, 7 and 8) on the aqueous solution of sodium dodecyl sulfate (SDS) in absence and presence of NaCl was examined using small-angle neutron scattering (SANS), dynamic light scattering (DLS), and viscosity measurements. Upon addition of C₁₂E _n , micellar size of SDS was found to increase significantly, and such micellar elongation was further enhanced in the presence of NaCl. Micellar growth is most significant in presence of shorter moieties of C₁₂E _n (e.g., n = 3, 4) as compared to higher ethereal oxygen content. The results of structural investigations with SANS and DLS to confirm this assumption are reported. The cloud point of C₁₂E _n has increased upon addition of SDS and decrease with NaCl, and a typical behavior is observed when both SDS and NaCl were present.     

Conformational free energy surface of the linear DPDPE peptide: cost of pre-organization for disulfide bond formation

We have calculated the free energy differences between four conformers of the linear form of the opioid pentapeptide DPDPE in aqueous solution. The conformers are Cyc, representing the structure adopted by the linear peptide prior to disulfide bond formation, β _C and β _E , two slightly different β-turns previously identified in unconstrained molecular dynamics simulations, and Ext, an extended structure. Our simulations indicate that β _E is the most stable of the studied conformers of linear DPDPE in aqueous solution, with β _C , Cyc and Ext having free energies higher by 2.3, 6.3, and 28.2 kcal/mol, respectively. The free energy differences of 4.0 kcal/mol between β _C and Cyc, and 6.3 kcal/mol between β _E and Cyc, reflect the cost of pre-organizing the linear peptide into a conformation conducive for disulfide bond formation. Such a conformational change is a pre-requisite for the chemical reaction of S–S bond formation to proceed. The relatively low population of the cyclic-like structure agrees qualitatively with observed lower potency and different receptor specificity of the linear form relative to the cyclic peptide, and with previous unconstrained simulation results. Free energy component analysis indicates that the moderate stability difference of 4.0–6.3 kcal/mol between the β-turns and the cyclic-like structure results from cancellation of two large opposing effects. In accord with intuition, the relaxed β-turns have conformational strain 43–45 kcal/mol lower than the Cyc structure. However, the cyclic-like conformer interacts with water about 39 kcal/mol strongly than the open β-turns. Our simulations are the first application of the recently developed multidimensional conformational free energy thermodynamic integration (CFTI) protocol to a solvated system, with fast convergence of the free energy obtained by fixing all flexible dihedrals. Additionally, the availability of the CFTI multidimensional free energy gradient leads to a new decomposition scheme, giving the contribution of each fixed dihedral to the overall free energy change and providing additional insight into the microscopic mechanisms of the studied processes. Received: 20 April 1998 / Accepted: 9 September 1998 / Published online: 7 December 1998     

Retinol fluorescence: a simple method to differentiate different bilayer morphologies

The fluorescence spectra of retinol obtained in bilayer structures of two different systems with dodecyl tetraethylenglycol ether are shown. A correlation between the fluorescence intensity of retinol and the different topologies of bilayers has been found. We have tested this correlation with the C₁₂E₄/benzyl alcohol/water system, and we have also applied this idea to the study of the lamellar phases of the C₁₂E₄/PEG/water system. The highest fluorescence intensity of retinol corresponds to unilamellar vesicles, while the lowest is observed for multilamellar vesicles. The kinetic study of the degradation of vitamin A in these media is also related to the different microstructures of the bilayers.     

The transition of three types of three-phase behavior in a temperature-composition space of water/C12EO6/propanol/heptane system

 The change of three-phase behavior of a water/hexaethylene-glycol dodecyl ether (C₁₂EO₆)/propanol/heptane system was studied with increasing temperature (30.0–48.9 °C). A cone-like three-phase body consisting of aqueous (W), surfactant (D_p), and oil (O) phases is formed in the composition tetrahedron at lower temperatures. The body is expanded with increasing temperature, and touches the water–C₁₂EO₆–heptane triangle (the base) at 44.8 °C. At about 45.6 °C the loci of the D_p and O phases meet and cut off at a critical double end point and the three-phase body separates into two bodies: one has a chiral shape and the other is unclosed. The unclosed body is transformed with the change of shape of the tie triangle on the base as temperature increases and leaves from the base at 48.9 °C. A closed-loop miscibility gap between middle surfactant (D^′ _p) and O phases or a cone-like three-phase body is formed inside the composition tetrahedron at higher temperatures. The roles of C₁₂EO₆ and propanol are also discussed. Received: 14 April 1998 Accepted: 15 July 1998     

Complexes of ammonia with propane and cyclopropane: electrostatic guidelines for ab initio treatment

A model based on the molecular electrostatic potential (MESP) is employed for the investigation of structures and energies of complexes of ammonia with propane and cyclopropane. The electrostatic model geometries are employed as starting points for an ab initio investigation at the self-consistent field and second-order M?ller-Plesset (MP2) levels. The most stable structures of C₃H₆..NH₃ and C₃H₈..NH₃ complexes have the interaction energies of 10.07 kJ/mol and 8.15 kJ/mol, respectively, at the MP2/6-31G(d,p) level. The energy rank order of the structures is not altered with the use of the 6-31++G(d,p) basis set, and the basis␣set superposition error has little effect. The interaction energy decomposition analysis shows that the electrostatic component is dominant over the other ones. MESP topography thus seems to offer valuable hints for predicting the structures of weakly bonded complexes. Received: 8 July 1998 / Accepted: 4 August 1998 / Published online: 2 November 1998     

Origins of two surfactant phases (D and Dp′) in a temperature-composition space of water/C12EO6 / propanol / heptane system: tricritical point and critical double end point

The origins of middle surfactant phases (D and Dp′) were investigated in the composition-temperature (49–73 °C) space of a water/hexaethyleneglycol dodecyl ether (C₁₂EO₆)/propanol/heptane system at atmospheric pressure. Two types of three-phase bodies exist in the dilute C₁₂EO₆ region of the four-component composition tetrahedron at 49.0 °C. A cone-like three-phase body consisting of aqueous (W), Dp′, and oil (O) phases becomes thinner with increasing temperature, and collapses into the superimposed critical tie lines (CTL) at 51.7 °C. One end of the superimposed CTL is a critical double end point where the closed-loop coexistence curve of the Dp′ and O phases disappears. The chiral three-phase body consisting of W, D, and O phases shrinks with increasing temperature, and finally vanishes at the tricritical point near 72.5 °C. The roles of C₁₂EO₆ and propanol are discussed and the conditions for the middle surfactant phases are discussed on the basis of the whole series of three-phase behavior. Received: 9 July 1998 Accepted in revised form: 25 August 1998     

Molecular dynamics simulations of sorption of organic compounds at the clay mineral/aqueous solution interface

The adsorption of trichloroethene, C₂HCl₃, on clay mineral surfaces in the presence of water has been modeled as an example describing a general program that uses molecular dynamics simulations to study the sorption of organic materials at the clay mineral/aqueous solution interface. Surfaces of the clay minerals kaolinite and pyrophyllite were hydrated at different water levels corresponding to partial and complete monolayers of water. In agreement with experimental trends, water was found to outcompete C₂HCl₃ for clay surface sites. The simulations suggest that at least three distinct mechanisms coexist for C₂HCl₃ on clay minerals in the environment. The most stable interaction of C₂HCl₃ with clay surfaces is by full molecular contact, coplanar with the basal surface. This kind of interaction is suppressed by increasing water loads. A second less stable and more reversible interaction involves adsorption through single-atom contact between one Cl atom and the surface. In a third mechanism, adsorbed C₂HCl₃ never contacts the clay directly but sorbs onto the first water layer. To test the efficacy of existing force field parameters of organic compounds in solid state simulations, molecular dynamics simulations of several representative organic crystals were also performed and compared with the experimental crystal structures. These investigations show that, in general, in condensed-phase studies, parameter evaluations are realistic only when thermal motion effects are included in the simulations. For chlorohydrocarbons in particular, further explorations are needed of atomic point charge assignments. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 144–153, 1998     

Liquid crystal and solution phases of sodium dodecyl-p-benzene sulphonate (NaLAS) and octa-oxyethylene glycol hexadecyl ether (C16E8): 1:1 mixtures in water

The liquid crystals and other phases formed when the mixed surfactant system sodium dodecyl-p-benzene sulphonate (NaLAS) and octa-oxyethylene glycol hexadecyl ether (C₁₆E₈, 1:1 by weight) is dispersed in water have been investigated using optical microscopy, X-ray diffraction and differential scanning calorimetry. Despite the fact that neat LAS is a multi-phase solid and C₁₆E₈ is a crystalline solid, when the two are mixed at temperatures above the melting temperature of the C₁₆E₈ with no water present, what appears to be a metastable gel phase formed containing only a small volume fraction of un-dissolved LAS (ca. 5%). Moreover, when water is added to the system, the phase behaviour of the mixture considerably differs to that of either of the individual components. We report a detailed phase study on this mixture here particularly focussing on the ‘neat’ mixture. The phase behaviour when water is added is also discussed. Particularly interesting is the presence of a micellar phase between the hexagonal and lamellar phases thought to be due to weak interactions between micelles during the transition from rods to discs. In addition, the presence of a low temperature intermediate phase is discussed.     

CH bond activation in the presence or absence of oxygen or nitrous oxide

The reaction of C₂H₆with lattice oxygen, O^2- (in the absence of gaseous oxygen), or “adsorbedℍ oxygen (in the presence of gaseous oxygen) over NiMoO₄ catalysts has been performed and compared to C₃H₈ activation. The results obtained indicate that adsorbed oxygen exhibits a higher reactivity to C₂H₆, while lattice oxygen is more reactive relative to C₃H₈. Kinetic studies of these two reactions in presence of molecular oxygen have indeed shown that the ethane oxidative dehydrogenation (ODH) is dependent on the oxygen partial pressure, whilst on the contrary propane ODH is not. In order to confirm the presence of “adsorbed” oxygen for ethane activation, ODH tests have been performed with N₂O. On increasing temperature, the O^- adsorbed species enhances the mild oxidation of ethane. The activation energy of ethane consumption E_C2H6, relative to propane (E_C3H8 = 133 kJ/mol) is 145 kJ/mol. A possible mechanism is proposed for the oxidative dehydrogenation of ethane. This revised version was published online in August 2006 with corrections to the Cover Date.     

Periodate oxidation analysis of carbohydrates: Part IX. Evaluation of the use of pyridine as reaction solvent for oxidation of water-insoluble carbohydrate materials

Oxidation of methyl glycopyranosides with periodic acid in pyridine was studied by analysis of the reaction products by the dithioacetal method. Both C₂—C₃ and C₃—C₄ bonds were cleaved yielding three types of dialdehydes;secondary attack of these dialdehydes by periodic acid did not occur. Oxidation in aqueous pyridine proceeded in normal Malapradian fashion, but more slowly than for oxidation in water. Molar proportions of aldehydes were theoretical, when methyl glycosides were oxidized with periodic acid in a 1:1 ($\text{v}\text{v}$) mixture of pyridine and water. The structures of carbohydrate moieties in a few saponins and glycolipids were confirmed by analysis of the oxidation products obtained under similar conditions.     

2-cyanopenta-(2E,4)-dienoic acid and its amide

Knoevenagel condensation of acrolein with NCCH₂COOK or NCCH₂CONH₂ in 1M aqueous solutions of K and Na phosphates gave 2-cyanopenta-(2E,4)-dienoic acid and its amide, respectively. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 363–365, February, 1998.     

An origin of a middle surfactant phase (Dp): A critical double end point in a water/polyoxyethylene alkyl ether/propanol/heptane system

 Phase behavior of water/hexaethyleneglycol dodecyl ether (C₁₂EO₆)/propanol/heptane system was investigated in a composition–temperature space (25–30 ^°C) at atmospheric pressure. A cone-like three-phase body consisting of aqueous (W), surfactant (Dp), and oil (O) phases is formed in the two-phase body of Wm (aqueous micellar phase)+O at 30.0 ^°C. With decreasing temperature the three-phase body becomes thinner and finally disappears at a critical double end point (CDEP) where the two critical end points of W and Dp phases are merged. The CDEP exists at about 26.2 ^°C (T _CDEP). The hydrophile–lipophile balance (HLB) of the mixed amphiphile changes towards lipophilic on addition of propanol. As a result, the Wm phase separates into two phases W+Dp above the T _CDEP. Further addition reduces the lipophobicity of aqueous media (or the solvophobicity of the mixed amphiphile), and the W and Dp phases are merged again. Below T _CDEP, since C₁₂EO₆ becomes much hydrophilic, the change of HLB lurks and a middle phase (Dp) cannot be observed. Received: 19 June 1997 Accepted: 20 March 1998     

Analysis of Chlormequat residues in grain using liquid chromatography-mass spectrometry (LC-MS/MS)

A fast, sensitive and specific method for routine determination of residues from Chlormequat (CAS no. 7003-89-6) is described. The method is based on a simple clean-up using an SPE-C₁₈ cartridge, high-performance liquid chromatography on a standard C₁₈ column (Spherisorb S5 ODS1) and specific detection and quantification by electrospray mass spectrometry (LC-MS/MS). ¹³C-Chlormequat was synthesised for use as internal standard. Samples were extracted with methanol – water – acetic acid. Internal standard and ammonium acetate were added before C₁₈-cartridge clean up and residues eluted with methanol – water – acetic acid, containing 50 mM ammonium acetate. Chromatographic separation was achieved using a solvent composed of acetonitrile – methanol – water – acetic acid (53:21:25:1 by volume), containing 50 mM ammonium acetate. Electrospray ionisation mass spectrometry was employed using m/z 58 (daughter ion of the Chlormequat quaternary ammonium ion, m/z 122) and m/z 61 (daughter ion of the ¹³C-Chlormequat quaternary ammonium ion, m/z 125) for quantification. The LC analysis time was 15 min and the limit of detection of the analytical method was 9 μg/kg. The performance of the method was demonstrated analysing grain material from an inter-comparison study. In Denmark the primary use of Chlormequat chloride (CCC, cycocel, or chlorocholin chloride, CAS no. 999-81-5) is for winter cereals and 11 such winter wheat samples from the Danish National Pesticide Survey were analysed. Residue contents were from below 0.01 up to 0.45 mg/kg, and thus below the EU maximum residue level of 2.0 mg/kg for wheat. Received: 22 December 1997 / Revised: 29 January 1998 / Accepted: 31 January 1998     

A potentiometric titration study on the dissociation of bile acids related to the mode of interaction between different head groups of nonionic surfactants with free bile salts upon mixed micelle formation in water

By constructing an elaborate set of potentiometric titration together with data analysis system, apparent acid dissociation indices (pK _a ^app ) for two bile acids were determined in the mixed surfactant system of bile salts (Sodium Deoxycholate, NaDC, and Sodium Chenodeoxycholate, NaCDC) with nonionic surfactants (Hexaethyleneglycol monon-dodecylether, C₁₂E₆, Decanoyl-N-methylglucamide, MEGA-10) in aqueous solution at ionic strength 1.5 as a function of mole fraction in the surfactant mixture. It was found that with increasing the bile salt concentration, pK _a ^app as well as pH showed an abrupt rise at a certain concentration of the bile salt being regardable as a critical micellization concentration (CMC) and reached a constant value at the range sufficiently higher than CMC for each pure bile salt system, meaning that the dissociation degree of carboxyl group in micelle is smaller than that in bulk. In the mixed systems of free bile salts with nonionic surfactants, the dissociation state of carboxyl groups in mixed micelles depends on the species of hydrophilic group of nonionic surfactants as well as on mole fraction in the surfactant mixture.     

Preparation of metal Niacin complexes and characterization using spectroscopic and electrochemical techniques

Metal complexes of Niacin (3-pyridin carboxylic acid) were prepared in aqueous medium and characterized by different physico-chemical methods. On the basis of elemental analysis the empirical formula of the complexes have been proposed as [Fe(C₆H₄NO₂)]Cl₂, [Co(C₆H₄NO₂)]Cl, [Zn(C₆H₄NO₂)]Cl, [Cd(C₆H₄NO₂)]Cl and [Hg(C₆H₄NO₂)]Cl. IR spectral data indicate that the metal-ligand bonding occurs through nitrogen atom of aromatic ring and oxygen atom of COO⁻-group. UV-visible spectra show that Fe(III) and Co(II) complexes show d-d electronic transition in addition to π → π*, n → π* and n → σ* transitions. The Fe(II) and Co(II) complexes are paramagnetic. QSTG analysis data strongly support the absence of water molecules in the complexes, and the weight of the residue corresponds to the respective metal oxides. Cyclic voltammetric studies suggest that the redox properties of Zn(II), Cd(II) and Hg(II) in their complexes are modified compared to the uncoordinated metal ion. The CV data also indicate that the charge transfer processes are not reversible.     

The catalyzed hydrosilation reaction: substituent effects

Ab initio electronic structure calculations using MP2 wavefunctions have been used to investigate a reaction path for the hydrosilation reaction catalyzed by divalent titanium [modeled by TiH₂, TiCl₂, and Ti(C₅H₅)₂]. Optimized structures and energies are presented. All model reactions predict a barrierless reaction path compared to a barrier of 78 kcal/mol for the uncatalyzed reaction. Received: 11 August 1998 / Accepted: 3 September 1998 / Published online: 23 February 1999     

A simple and mild derivatization method for hydroxyl compounds using condensation agent carbazole-9-N-(2-methyl)-acetyl-benzene-disulfonate and its application for the determination of volatile alcohols from plasma by HPLC with fluorescence detection

A simple and sensitive HPLC method for the determination of hydroxyl compounds including volatile alcohols from spiked plasma, using a fluorescent condensation agent, namely carbazole-9-N-(2-methyl)-acetyl-benzene-disulfonate (CMABS), has been developed. A mixture of alcohols and pyridine in dichloromethane was treated with CMABS to give a quantitative yield of esters. The maximum fluorescence emissions for the derivatized alcohols are at 365 nm (λ_ex 335 nm). Studies on derivatization conditions indicate that alcohols react very fast with CMABS in presence of pyridine in dichloromethane to give the corresponding fluorescent derivatives. The method, in conjunction with a multi-step gradient, offers a baseline resolution of the common alcohol derivatives on a reversed-phase C₁₈ column, which is more convenient and more efficient than previous methods which require the prior conversion of the carboxylic acids to the acyl chlorides. The application of this method to the analysis of volatile alcohols in plasma was also investigated. The LC separation shows good selectivity and reproducibility for alcohol derivatives. The relative standard deviations ?(n = 5) for 100 pmol of each alcohol are < 4%. The detection limits are at the fmol level for C₁–C₃ alcohols and pmol level for C₄–C₉ alcohols. Received: 9 November 1998 / Revised: 3 May 1999 / Accepted: 6 May 1999