The interaction between poly(N-isopropylacrylamide) and salts in aqueous media: The “salting-out” phenomenon as studied by attenuated total reflection/fourier transform infrared spectroscopy

The effect of two strong salting-out salts (Na₂SO₄ and K₂SO₄) on the temperature-induced phase-separation process in aqueous solutions of poly(N-isopropylacrylamide) (PNIPA) was examined by attenuated total reflectance/Fourier transform infrared spectroscopy, differential scanning calorimetry, and viscosity measurements. On the basis of these measurements, a detailed scenario of the phase-separation process was deduced. The phase-separation scenario of solutions containing PNIPA and water was altered in the presence of sulfate ions. Here, the sulfate ions induced partial intrachain collapse, manifested by a relatively compact structure well below the lower critical solution temperature. This led to a more gradual, smooth phase transition, with temperature-resolved intrachain collapse and interchain aggregation and a lesser extent of hysteresis. Although at the macrolevel one may not be able to differentiate among various scenarios altering the solvent into a poor solvent, the aforementioned microlevel measurements provided a way to expose the difference between raising the temperature and adding cosolutes. Follow-up studies on the effect of salting-in salts will be presented. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 33–46, 2004     

Excess enthalpies of some 2-alkanone + 1-chloroalkane binary mixtures at 25 and 35°C

Excess molar enthalpies h^E at 25 and 35° C and atmospheric pressure, are reported for the binary mixtures formed by a 2-butanone and 2-pentanone with 1-chlorobutane, 1-chloropentane, 1-chlorohexane, or 1-chlorooctane. The h^E values for all the mixtures are positive, increasing as the 1-chloroalkane length increases and as the ketone length decreases. Excess molar enthalpies depend slightly on the temperature. The experimental values together with those from the literature were used to calculate the interaction parameters for the Dang-Tassios version of the UNIFAC model.Communicated at the Festsymposium celebrating Dr. Henry V. Kehiaian's 60^th birthday, Clermont-Ferrand, France, 17–18 May 1990.     

Excess enthalpies of (methyl propanoate or methyl pentanoate + 1-alkanol) at 298.15 K

The excess molar enthalpies H_m^E of methyl propanoate or methyl pentanoate + 1-butanol, + 1-hexanol, + 1-octanol, and + 1-decanol have been determined experimentally at 298.15 K using a Calvet microcalorimeter. For all these mixtures H_m^E > 0; the values increase with the chain length of the alkanol but decrease as the ester chain lengthens.     

A novel microporous copper silicate: Na2Cu2Si4O11.2H2O

The synthesis and structural characterisation of a thermally stable novel three-dimensional microporous copper silicate open-framework are described; the material is capable of undergoing reversible zeolitic water removal without destruction of the framework.     

X-ray diffraction and solid-state NMR studies of a germanium binuclear complex

A compound formulated as (C4H12N2)[Ge2(pmida)2(OH)2] x 4 H2O (where pmida(4-) = N-(phosphonomethyl)iminodiacetate and C4H12N2(2+) = piperazinedium cation), containing the anionic [Ge2(pmida)2(OH)2]2- complex, has been synthesised by the hydrothermal approach and its structure determined by single-crystal X-ray diffraction analysis. Several high-resolution solid-state magic-angle spinning (MAS) NMR techniques, in particular two-dimensional 1H-X(13C,31P) heteronuclear correlation (HETCOR) and 1H-1H homonuclear correlation (HOMCOR) experiments incorporating a frequency-switched Lee-Goldburg (FS-LG) decoupling scheme, have been employed for the first time in such a material. Using these tools in tandem affords an excellent general approach to study the structure of other inorganic-organic hybrids. We assigned the NMR resonances with the help of C...H and P...H internuclear distances obtained through systematic statistical analyses of the crystallographic data. The compound was further characterised by powder X-ray diffraction techniques, IR and Raman spectroscopy, and by elemental and thermal analyses (thermogravimetric analysis and differential scanning calorimetry).     

Thermodynamic properties of the ternary system MTBE+1-propanol+hexane

Experimental excess molar enthalpies and excess molar volumes of the ternary system x₁MTBE+x₂1-propanol+(1-x₁-x₂) hexane and the involved binary mixtures have been determined at 298.15 K and atmospheric pressure. Excess molar enthalpies were measured using a standard Calvet microcalorimeter, and excess molar volumes were determined from the densities of the pure liquids and mixtures, using a DMA 4500 Anton Paar densimeter. The UNIFAC group contribution model (in the versions of Larsen et al., and Gmehling et al.) has been employed to estimate excess enthalpies values. Several empirical expressions for estimating ternary properties from experimental binary results were applied.     

Indirect determination of the pesticide dimethoxydithiophosphate in an FIA-AAS system with liquid-liquid back-extraction

A method has been developed for the determination of dimethoxydithiophosphate (DDTP) by liquid-liquid extraction in a flow-injection analysis (FIA) system with detection by atomic-absorption spectrometry (AAS). It is based on the formation of the Cu(DDTP)(2) complex and its extraction into chloroform, and back-extraction of the copper with an ammonia buffer (pH 10). The method uses small amounts of samples, avoids handling errors and is fast and highly reproducible. It features a detection limit of 0.39 ppm DDTP (2.45 x 10(-6)M in the organic phase) and a relative standard deviation of 1.6%. The method has been applied to the determination of the organophosphorus pesticide malathion in an agricultural formulation.     

On the Stability of the Schiff Bases of Pyridoxal 5′-Phosphate with Polypeptides Containing L-Lysine

We determined the apparent equilibrium constant of formation, K_pH, of the Schiff bases of pyridoxal 5′-phosphate (PLP) and poly- and copolymers containing L -lysine, as a function of pH at 25° and a constant ionic strength of 0.1 M . The K_pH values obtained at acidic and neutral pH were larger that those reported for Schiff bases of PLP and hexylamine. We determined calorimetrically ΔH of formation of Schiff bases of PLP and poly(L -lysine) (?4.5′kcal/mol), and PLP and hexylamine (?3.4 kcal/mol) at pH 7.00. Semi-empirical theoretical calculations (INDO and AMI methods) of a model compound of Schiff base of PLP and polypeptide containing L -lysine show the capability of specific interactions between groups of PLP and the peptide skeleton.