Conductance behaviour of HCl in water-ethylene glycol, water-diethylene glycol and ethylene glycol-diethylene glycol mixtures

The conductance behaviour of HCl in water-ethylene glycol, water-diethylene glycol and ethylene glycol-diethylene glycol mixtures was investigated in the complete range of solvent compositions of 25°C by applying the three-parameter conductance equation. No appreciable association of the acid was observed in any of the mixed solvents. The large decrease ofΛ ₀ andΛ ₀ η ₀ of the acid in the early and end composition region of the mixed solvents has been attributed to the drastic structural changes brought about by the addition of the organic component in the aqueous solvent mixtures and by the addition of diethylene glycol in the case of ethylene glycol-diethylene glycol mixtures.     

Crystal structures of ethylene glycol and ethylene glycol monohydrate

We have carried out a neutron powder diffraction study of deuterated ethylene glycol (1,2-ethanediol), and deuterated ethylene glycol monohydrate with the D2B high-resolution diffractometer at the Institut Laue-Langevin. Using these data, we have refined the complete structure, including all hydrogen atoms, of the anhydrous phase at 220 K. In addition, we have determined the structure of ethylene glycol monohydrate at 210 K using direct space methods. Anhydrous ethylene glycol crystallizes in space-group P2(1)2(1)2(1) with four formula units in a unit-cell of dimensions a = 5.0553(1) ?, b = 6.9627(1) ?, c = 9.2709(2) ?, and V = 326.319(8) ?(3) [ρ(calc)(deuterated) = 1386.26(3) kg m(-3)] at 220 K. Ethylene glycol monohydrate crystallizes in space-group P2(1)/c with four formula units in a unit-cell of dimensions a = 7.6858(3) ?, b = 7.2201(3) ?, c = 7.7356(4) ?, β = 92.868(3)°, and V = 428.73(2) ?(3) [ρ(calc)(deuterated) = 1365.40(7) kg m(-3)] at 210 K. Both the structures are characterized by the gauche conformation of the ethylene glycol molecule; however, the anhydrous phase contains the tGg' rotamer (or its mirror, g'Gt), whereas the monohydrate contains the gGg' rotamer. In the monohydrate, each water molecule is tetrahedrally coordinated, donating two hydrogen bonds to, and accepting two hydrogen bonds from the hydroxyl groups of neighboring ethylene glycol molecules. There are substantial differences in the degree of weak C-D···O hydrogen bonding between the two crystals, which calls into question the role of these interactions in determining the conformation of the ethylene glycol molecule.     

Polyethylene glycol

The increasing demand of synthetic oligonucleotides for therapeutic and diagnostic purposes can be hardly satisfied by simply upscaling the commercial synthesizers. The introduction of a liquid-phase method that utilizes a polymeric support soluble into the reaction media can overcome the shortcomings related to the heterogeneity of the solid phase and allow a convenient large-scale process. Recently we have proposed a new synthetic approach for the oligonucleotide production that utilizes polyethylene glycol or PEG as soluble supporting polymer. We call this method High-Efficiency Liquid Phase or HELP. This approach preserves the advantages of a homogeneous synthesis in solution and adds an easy purification step of all the intermediates, mimicking the solid-phase procedure. In fact, reagent excess and byproducts can be eliminated by a simple precipitation-and-filtration step at the end of each synthetic cycle. Since all the reactions take place in solution, the scale-up of the process is easily predictable. Various synthetic protocols have been tested and optimized for the oligonucleotide production, up to the antisense-size level. After the phosphotriester and the phosphoramidite chemistry, the H-phosphonate approach is now under development. The possibility of an efficient automation of the whole process is also investigated.     

Identification and quantification of polyethylene glycol types in polyethylene glycol methyl ether and polyethylene glycol vinyl ether

Quantitative determination of polyethylene glycol (PEG) impurities in two monofunctional polyglycol types, PEG methyl ether (M-PEG) and PEG vinyl ether (V-PEG), has been carried out by reversed-phase liquid chromatography with evaporative light scattering detection (ELSD). In addition to optimizing the resolution between PEG and monofunctional PEG peaks, the major focus has been to determine the molecular weights of PEG impurities in M-PEG and V-PEG of diverse molecular weights. The latter is achieved by examining liquid chromatography–mass spectrometry (LC–MS) mass spectra of both monofunctional PEG and PEG in several cases, and matching peak retention times with those of available PEG standards for all M-PEG and V-PEG sample types. This information is helpful in selecting the appropriate PEG standard to determine PEG content in each sample type. ELSD response factors for various PEG standards have also been compared. It has been found that PEG standards with molecular weights from 1000 Da to 8000 Da show responses that are within 10% of each other. However, a low molecular weight PEG such as PEG 400, provides approximately 30% less response compared to its higher molecular weight counterparts.     

Relative permittivity of the binary mixtures of 2-methoxyethanol with diethylene glycol,triethylene glycol,tetraethylene glycol,and polyethylene glycol 200 at various temperatures

Relative permittivities at T = (293.15, 298.15, and 303.15) K in the binary liquid mixtures of 2-methoxyethanol with diethylene glycol, triethylene glycol, tetraethylene glycol, and polyethylene glycol 200 have been measured over the entire mixture compositions. The relative permittivity deviations (Δε) were calculated from these experimental data. The results are discussed in terms of intermolecular interactions and structure of studied binary mixtures.     

Viscosimetric and ultrasonic studies of intermolecular interactions of 2-methoxyethanol with diethylene glycol,triethylene glycol and tetraethylene glycol binary mixtures

The viscosities at T = (293.15, 298.15 and 303.15) K and ultrasonic speeds at T = 298.15 K in the binary liquid mixtures of 2-methoxyethanol with diethylene glycol, triethylene glycol and tetraethylene glycol have been measured over the entire mixture compositions. From the experimental data, deviations in the viscosity (Δη), ultrasonic speed (Δu), and excess energies of activation for viscous flow (ΔG* ^E ) have been calculated. The viscosity data were correlated with equations of Hind et al., Grunberg and Nissan, Frenkel, and McAllister. The results are discussed in terms of intermolecular interactions and structure of studied binary mixtures.     

Tough crystalline blends of polylactide with block copolymers of ethylene glycol and propylene glycol

The effect of crystallinity of polylactide (PLA) on the structure and properties of tough PLA blends with PEG-b-PPG-b-PEG block copolymers was studied. PLA was melt blended with a set of the copolymers with varying ratio of the hydrophilic (PEG) and hydrophobic (PPG) blocks. Although the blend phase structure depended on the copolymer molar mass and PEG content, as well as on the copolymer concentration in the blend, crystallinity also played an important role, increasing the copolymer content in the amorphous phase and enhancing phase separation. The influence of crystallinity on the thermal and mechanical properties of the blends depended on the copolymer used and its content. The blends, with PLA crystallinity of 25 ÷ 34 wt%, exhibited relatively high glass transition temperature ranging from 45 to 52 °C, and melting beginning above 120 °C. Although with a few exceptions crystallinity worsened the drawability and toughness, these properties were improved with respect to neat crystalline PLA in the case of partially miscible blends, in which fine liquid inclusions of the modifier were dispersed in PLA rich matrix. About 20-fold increase of the elongation at break and about 4-fold increase of the tensile impact strength were reached at a small content (10 wt%) of the modifier. Moreover, crystallinity decreased oxygen and water vapor transmission rates through neat PLA and the blend, and the barrier property for oxygen of the latter was better than that of neat polymer.     

Mechanism of the three-dimensional polymerization of glycol methacrylates. II. The system glycol monomethacrylate–glycol dimethacrylates–solvents

The three-dimensional polymerization of the system glycol monomethacrylate–glycol dimethacrylates–solvents has been studied. The kinetic dependences thus obtained were interpreted in terms of the dependence of rate constants of the individual reactions on the properties of the medium used. The three-dimensional polymer formed was characterized in the range from medium to the highest conversions.     

Critical behavior and interfacial tension of mixtures of propylene glycol and ethylene glycol oligomers

This investigation presents an analysis of the critical behavior of mixtures of oligomers of propylene glycol, PG₁₇, and ethylene glycol, EG_n, withn=3, 4, 5, 6.4, 8.7, 12.1 and 22.1. The critical coordinates, _c andT _c were determined from the phase diagrams. The critical compositions compare very well with the Huggins-Flory predictions. The interaction parameter _n is around one for EG₃, EG₄ and EG₅ and it increases up to two for the higher oligomers. The break in the interaction parameter also corresponds to a minimum in the critical temperature. The phase diagrams and the interfacial tension were used to get the critical exponents and , respectively. The data were analysed with two approaches. First, from the temperature dependence of the length of the tie-lines and of the interfacial tension up to the upper critical solution temperature, UCST. Second, with the data at 30°C using the critical temperature of the systems as the variable. The first method led to =0.39±0.05 in good agreement with the result of the second method, =0.37±0.04. The exponents for the interfacial tension, , determined with the first method for PG₁₇ with EG_6.4, EG_8.7 and EG_12.1 are =1.66±0.11, 1.46±0.25 and 1.73±0.18, respectively. The second method led to =1.17±0.14. The critical exponents are compared to mean field and ising-3D predictions.     

Viscosity of binary mixtures of 2-ethoxyethanol with ethylene glycol,diethylene glycol,triethylene glycol and tetraethylene glycol systems at T = (293.15, 298.15 and 303.15) K

Viscosities, at T = 293.15, 298.15 and 303.15 K, in the binary mixtures of 2-ethoxyethanol with ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol have been measured as a function of composition. From the experimental data the deviations in the viscosity have been calculated. The viscosity data, at T = 298.15 K, were correlated with equations of Hind et al., Grunberg and Nissan, and Frenkel. The results are discussed in terms of intermolecular interactions and structural properties of studied binary mixtures.     

聚乙二醇二丁二酸酯的合成

聚乙二醇在药物合成上有很广泛的用途,但其端羟基的活性相对较低,直接应用受到限制.若将羟基活化为羧基则可以扩大其应用范围;尤其是在合成二聚物时,将疏水链换成亲水的聚乙二醇二丁二酸酯链可以增加桥链的亲水性.为此,以聚乙二醇、丁二酸酐为反应物,以吡啶为溶剂,分别合成了一缩二乙二醇二丁二酸酯、二缩三乙二醇二丁二酸酯、三缩四乙二...     

Kinetic analysis of glycol mixtures

A kinetic method of analysis is outlined for the determination of two-component mixtures of ethane-diol, propane-1,2-diol and butane-2,3-diol, based on the measurement of reaction rates with lead tetraacetate in acetic acid solution. The method is of limited application only for ethane- and propane-diol mixtures but should prove useful for the analysis of butane-diol/propane-diol and butanediol/ethane-diol systems, the lower limit of concentration ratio being 1:100 and 1:1000 respectively.     

Structure of liquid ethylene glycol

The structure of liquid ethylene glycol (EG) was studied by the vibrational spectroscopy and isothermal compressibility techniques. Raman spectra were recorded at 296 K, IR spectra were measured at 296 and 90 K, and the isothermal compressibility was measured over a pressure range of 0.1–300 MPa. The results obtained were compared with analogous data for water. The structure of liquid EG is discussed using the available literature data on the conformation of its molecule in the gas phase and X-ray diffraction data for crystalline EG. It was concluded that liquid EG has a three-dimensional network of hydrogen bonds, which is more uniform and less mobile compared to water, a feature that explains why the viscosity of EG is high.     

Kinetics of propylene glycol hydrochlorination

The kinetics of hydrochlorination of propylene glycol with hydrogen chloride, both noncatalytic and catalyzed by acetic acid, has been investigated. The type of kinetic equation, pre-exponential factor, activation energy, and empirical coefficients characterizing the chloride ion hydration effect on the rate of propylene glycol hydrochlorination have been determined.