Surfactant effect on the lower critical solution temperature of poly(organophosphazenes) with methoxy-poly(ethylene glycol) and amino acid esters as side groups

 The surfactant effect on the lower critical solution temperature (LCST) of thermosensitive poly(organophosphazenes) with methoxy-poly(ethylene glycol) and amino acid esters as side groups was examined in terms of molecular interactions between the polyphosphazenes and surfactants including various anionic, cationic, and nonionic surfactants in aqueous solution. Most of the anionic and cationic surfactants increased the LCST of the polymers: the LCST increased more sharply with increasing length and hydrophobicity of the hydrophobic part of the surfactant molecule. The ΔLCSTs (T _0.03M− T _0M), the change in the LCST by addition of 0 and 0.03 M sodium dodecyl sulfate (SDS), were found to be 7.0 and 14.5 °C for the polymers bearing ethyl esters of glycine and aspartic acid, respectively. The LCST increase of poly(organophosphazene) having a more hydrophobic aspartic acid ethyl ester was 2 times larger compared with that of the polymer having glycine ethyl ester as a side group. The binding behavior of SDS to the polymer bearing glycine ethyl ester as a hydrophobic group was explained from the results of titration of the polymer solutions containing SDS with tetrapropylammonium bromide. Graphic models for the molecular interactions of polymer/surfactant and polymer/surfactant/salt in aqueous solutions were proposed. Received: 17 February 2000/Accepted: 25 April 2000     

Improvement of an old spectrophotometric method for the microdetermination of ascorbic acid by the use of a micellar medium

₃]²⁺. Whereas the initial method is carried out in an aqueous solution, the improved one employs an aqueous micellar medium formed by the cationic surfactant cetylpyridinium bromide (CPBR). The λmax in both methods is the same, i.e. 510 nm. The mean apparent molar absorptivity (ɛ) and Sandell’s sensitivity (Ss) were calculated as ɛ=2.10×10⁴ Lmol^-1 cm^-1 and Ss=8.37 ng cm^-2 for the initial procedure, and ɛ=2.62×10⁴ Lmol^-1 cm^-1 and Ss=6.72 ng cm^-2 for the improved one. The regression line equation for the improved method was: A=1.487×10^-1C −1.415×10^-2 (r=0.9998). The accuracy and the precision of the improved method were investigated and the conclusions were satisfactory. The results obtained for ASCA by both the described method and an official one, were statistically compared by means of the Student’s t-test and by the variance ratio F-test; and no significant difference was observed. Received: 15 January 1996/Revised: 7 March 1996/Accepted: 13 March 1996     

Determination of As, Cd, and Pb in epicuticular waxes of pine and spruce needles by ETAAS

 Waxes were separated from needles by chloroform washing, drying and dissolving the residue in tetrahydrofuran (THF). Both a THF solution of the wax and an aqueous solution of the Pd-Mg matrix modifier were sampled directly into the graphite tube. The reaction conditions were optimised for the wax concentration of 45 mg ml^-1 in THF and the Pd:Mg ratio of 1:1 in the matrix modifier. The atomisation and charring temperatures for As, Cd and Pb were the same as those recommended for analysis of aqueous solutions except the charring temperature of Cd takes 200 °C lower. The characteristic masses for As (26 pg), Cd (0.5 pg) and pb (9 pg) are also comparable to published data. The parameters of calibration curves were identical for all three elements dissolved either in clear THF or in the wax solution. Elemental concentrations were found to range from 0.1 to 1.0 mg g^-1, increasing with needle age for As, Pb but not Cd. Received: 20 September 1996 / Revised: 14 November 1996 / Accepted: 13 December 1996     

Dielectric behaviour of Gelatin solutions and Gels

 Sol and Gel state properties of aqueous gelatin solutions of concentrations 4%, 6%, 8% and 10% (w/v) have been investigated through dielectric relaxation studies done at various temperatures in the range T=20–60 °C carried out over a frequency range f=20 Hz–10 MHz and no relaxation of any nature was observed. The sharp transition observed at the gelation temperature T _gel provided an excellent matching with the same measured through differential scanning calorimetry (DSC). The capacitance (C _p) values above f=100 kHz became increasingly negative as the gel was melted to the sol state. However, in the gel state C _p was found to be almost independent of temperature for frequencies above 100 kHz. At frequencies lower than 10 kHz, C _p measured was ∼10⁵ F, implying pronounced interfacial polarization either due to electro-chemical reaction or because of ions getting trapped at some interface within the bulk. Received: 10 February 1997 Accepted: 2 September 1997     

Determination of traces of uranium and thorium in (Ba, Sr) TiO3 ferroelectrics by inductively coupled plasma mass spectrometry

 Traces of uranium and thorium in barium(II), strontium(II) titanate ((Ba, Sr)TiO₃) ferroelectric materials were determined by inductively coupled plasma mass spectrometry (ICP-MS). Samples were completely dissolved by a mixture of 1.4% H₂O₂ and 1.0 mol⋅l^-1 HNO₃. For a complete separation of the analytes from the matrix elements, a two step separation technique involving leaching and anion-exchange was applied. By the leaching step with HNO₃ more than 90% of the matrix can be removed whereas the analytes completely remained in the solution. The anion-exchange step was carried out on a BIO⋅RAD AG1-X8 column with a mixture of 1.0 mol⋅l^-1 HF and 0.5 mol⋅l^-1 HNO₃ as eluent. The content of uranium and thorium was subsequently measured by ICP-MS. The detection limits (D.L.) obtained were 0.043 ng g^-1 and 0.035 ng g^-1 for U and Th, respectively. The reproducibility was satisfactory with a relative standard deviation of less than 3% (at the 1 ng g^-1 level, n=5). The matrix concentrations in the final solution were reduced to the sub-μg ml^-1 level which is in the range of the detection limits of USN-ICP-AES (ultrasonic nebulization-ICP-atomic emission spectroscopy). The method was successfully applied to the determination of uranium and thorium in three synthetic (Ba, Sr)TiO₃ samples spiked with the analytes at levels of 1, 5 and 10 ng g^-1 and three (Ba, Sr)TiO₃ ferroelectric samples containing sub-ng g^-1 levels of the analytes. Received: 26 February 1996/Revised: 28 May 1996/Accepted: 5 June 1996     

Determination of traces of uranium and thorium in (Ba, Sr) TiO3 ferroelectrics by inductively coupled plasma mass spectrometry

 Traces of uranium and thorium in barium(II), strontium(II) titanate ((Ba, Sr)TiO₃) ferroelectric materials were determined by inductively coupled plasma mass spectrometry (ICP-MS). Samples were completely dissolved by a mixture of 1.4% H₂O₂ and 1.0 mol⋅l^-1 HNO₃. For a complete separation of the analytes from the matrix elements, a two step separation technique involving leaching and anion-exchange was applied. By the leaching step with HNO₃ more than 90% of the matrix can be removed whereas the analytes completely remained in the solution. The anion-exchange step was carried out on a BIO⋅RAD AG1-X8 column with a mixture of 1.0 mol⋅l^-1 HF and 0.5 mol⋅l^-1 HNO₃ as eluent. The content of uranium and thorium was subsequently measured by ICP-MS. The detection limits (D.L.) obtained were 0.043 ng g^-1 and 0.035 ng g^-1 for U and Th, respectively. The reproducibility was satisfactory with a relative standard deviation of less than 3% (at the 1 ng g^-1 level, n=5). The matrix concentrations in the final solution were reduced to the sub-μg ml^-1 level which is in the range of the detection limits of USN-ICP-AES (ultrasonic nebulization-ICP-atomic emission spectroscopy). The method was successfully applied to the determination of uranium and thorium in three synthetic (Ba, Sr)TiO₃ samples spiked with the analytes at levels of 1, 5 and 10 ng g^-1 and three (Ba, Sr)TiO₃ ferroelectric samples containing sub-ng g^-1 levels of the analytes. Received: 26 February 1996/Revised: 28 May 1996/Accepted: 5 June 1996     

An effective cross-linking of polymer layer on monodisperse, poly(maleic anhydride-styrene)-modified colloidal silica particles and properties of the composite

Summary  The cross-linkings of the surface polymer layer on mono disperse, poly(maleic anhydride-styrene)-modified silica particles by the reaction with diisocyanate were studied. The extent of cross-linking was estimated by the weight decrease by immersing the particles in the buffer solution of pH 2.0, 4.0 and 9.0 at a room temperature for 24 h. The reaction of the polymer-modified silica with 1,6-diisocyanatohexane afforded relatively stable composite particles which lost less than 5 wt% of the polymer in aqueous solution in the pH range 2.0–9.0. The diisocyanate was a preferable cross-linker to 2,4-diisocyanatotoluene in terms of stability in acidic or basic aqueous solution. The flexibility of the cross-linker molecule possibly plays an important role in the cross-linking reaction. The carboxyl and amino groups were formed by treating the cross-linked composite particles with diluted HCl solution; 5–6 and 0.5–1.1 μmol g^-1, respectively. The cross-linked composite particles exhibited the characteristic property of ζ-potential, −44 to −47 mV and −102 to −107 mV in a neutral aqueous solution and ethanol, respectively. Received: 26 May 1997 Accepted: 4 August 1997     

Influence of molecular weight on the microhardness of poly(ethylene terephthalate)

 Poly(ethylene terephthalate) (PET) was annealed in vacuum at different temperatures (190–260 °C) for different times (10 min–24 h) in order to examine the mechanical properties (microhardness) of PET samples with a wide range of molecular weights (10 000–120 000). Short annealing times result in a twofold decrease in mol. wt. due to hydrolytic decomposition. However, long annealing times give rise to a substantial molecular weight increase. It is found that microhardness (H) rises linearly with the degree of crystallinity obtained during up-grading of mol. wt. and its extrapolation leads to H-values of completely crystalline PET, H ^PET _c=405 MPa for samples with conventional mol. wt. and of 426 MPa for samples with mol. wt. higher than 30 000. It is shown that the increase of mol. wt. for each set of samples with a given range of degree of crystallinity also causes a slight increase of H. The influence of mol. wt. upon hardness is discussed in the light of the changes in the physical structure (crystallinity, crystal thickness) which is formed at given heat treatment conditions. Received: 29 April 1997 Accepted: 23 September 1997     

Physicochemical characterization of a novel surfactant peptide containing an arginine cation and laurate anion

 A novel surfactant peptide consisting of an arginine cation with laurate anion has been synthesized, purified and characterized. The critical micellar concentration (cmc) of peptide in aqueous solutions has been determined using spectroscopic techniques and is found to increase from 0.06 to 0.11 mM with increasing temperature (15–45 °C). Cmc is also determined in the presence of salts like NaCl, KCl and sodium acetate and it is found that these electrolytes hinder aggregation with a significant increase in the case of sodium acetate. The aggregation number of the surfactant peptide has been determined using fluorescence quenching measurements and is observed to decrease from 14 to 6 with increasing temperature (15–45 °C). The standard free energy change (ΔG ⁰ _m) and standard enthalpy change (ΔH ⁰ _m) of the peptide aggregate are found to be negative with a small positive value for standard entropy change (ΔS ⁰ _m). The peptide aggregate seems to undergo phase transition above 50 °C as observed from UV–vis and fluorescence spectroscopy. From pyrene binding studies, it is shown that the interior dielectric constant increases from 5.08 at 34 °C to 8.77 at 50 °C and further decreases with increase in temperature indicating a phase change at 50 °C. Also, the ratio of excimer intensity to monomer intensity, which is a measure of microviscosity of the aggregate, decreases with increase in temperature with a change at 50 °C indicating a phase change. Received: 14 February 1997 Accepted: 13 August 1997     

Boronic acid-facilitated α-hydroxy-carboxylate anion transfer at liquid/liquid electrode systems: the EICrev mechanism

The transfer of the α-hydroxy-carboxylates of glycolic, lactic, mandelic and gluconic acid from the aqueous electrolyte phase into an organic 4-(3-phenylpropyl)-pyridine (PPP) phase is studied at a triple-phase boundary electrode system. The tetraphenylporphyrinato complex MnTPP dissolved in PPP is employed to drive the anion transfer reaction and naphthalene-2-boronic acid (NBA) is employed as a facilitator. In the absence of a facilitator, the ability of α-hydroxy-carboxylates to transfer into the organic phase improves, consistent with hydrophobicity considerations giving relative transfer potentials (for aqueous 0.1 M solution) of gluconate>glycolate>lactate>mandelate. In the presence of NBA, a shift of the reversible transfer potential to more negative values is indicating fast reversible binding (the mechanism for the electrode process is EIC_rev) and the binding constants are determined as K _glycolate = 2 M⁻¹, K _mandelate = 60 M⁻¹, K _lactate = 130 M⁻¹ and K _gluconate = 2,000 M⁻¹. The surprisingly strong interaction for gluconate is rationalised based on secondary interactions between the gluconate anion and NBA.     

Colloidal hydrolysis products of SbCl3 in acidic solutions

 The hydrolysis of SbCl₃ in hydrochloric acid solution (2.0 mol dm^-3 HCl) at 0 °C yields an amor-phous product consisting of uniform spherical particles (d∼0.5 μm), which on continuous aging at the same temperature transform to larger crystals, indicated by XRD to be Sb₄O₅Cl₂. In contrast, in the same solution kept at 25 °C crystalline particles of the same composition form directly after an induction period and then grow with time. The final products, obtained at 0 °C and 25 °C consist of aggregated subunits. These powders on calcination in nitrogen are converted to Sb₂O₃ and in air to Sb₂O₄. Received: 23 June 1997 Accepted: 1 July 1997     

Aqueous solution behavior of alkali-soluble polyethylene periodic polyelectrolyte, poly(ethylene- per-ethylene-per-acrylic acid)

A sequence-ordered, periodic copolymer of ethylene, ethylene, and acrylic acid, poly (ethylene-per-ethylene-per-acrylic acid) (PEEA), with M _w=1.44×10⁵ has been synthesized by alternating copolymerization of 1,3-butadiene and methyl acrylate, followed by hydrogenation and hydrolysis. Aqueous solution and dissociation properties of the alkali-soluble PEEA were explored by potentiometric titration and intrinsic viscosity at 25 °C. The pH values of PEEA were almost constant (pH = 6.48 ∼ 6.55) with an increasing degree of dissociation (α) from 0.3 to 0.8 at C _s=50 mN NaCl. Correspondingly, the plots of negative logarithm of apparent dissociation constant (pK _a) against α showed a reversed S-shape curve over the whole α, indicating an extensive precipitation and subsequent tran-sition from compact to coiled conformation. The intrinsic viscosity steeply increased with α above 0.4 up to 9.97 dl/g at α = 1.0. Good agreement between the observed electrostatic potential and that calculated from the rod model with a smeared charge density was observed in the region of α higher than 0.9. The dissociation and dissolution processes of PEEA with neutralization in water were described. Received: 14 April 1998 Accepted: 3 June 1998     

Determination of trace elements in AR grade alkali salts after preconcentration by column solid-phase extraction on TiO2 (anatase)

 Column solid-phase extraction using TiO₂ (anatase) as a solid sorbent was applied to preconcentrate traces of Cd, Co, Cu, Fe, Mn, Ni and Pb from AR grade alkali salts prior to their measurements by atomic absorption spectrometry (AAS). Multi-element preconcentration was achieved from NaCl, KCl, KNO₃, NaNO₃, CH₃COONa, NaHCO₃ and Na₂CO₃ solutions, whereas the sorption of trace elements from phosphates and sulfates is not quantitative. Optimal conditions (recoveries of the analytes >95%) for solid-phase co-extraction of the most common heavy metal ions are proposed. The conditions for quantitative and reproducible elution and subsequent AAS are established. A method of determination of trace elements in different salts is proposed. It is characterized by precision, reproducibility and a high preconcentration factor. The solid-phase extraction by TiO₂, combined with ETAAS allows the determination of 0.1 ng g^-1 Cd, 2 ng g^-1 Co, 1 ng g^-1 Cu and Ni, 0.5 ng g^-1 Mn and 0.4 ng g^-1 Pb. Received: 1 April 1996/Revised: 24 June 1996/Accepted: 9 July 1996     

Preparation and ionic conductivity of poly(ethylene oxide) oligomers having thiolate groups on the chain ends

Poly(ethylene oxide) (PEO) oligomers having alkali metal thiolate groups on the chain ends (PEO _m -S⁻M⁺) were prepared as an ion conductive matrix. The molecular weight of the PEO part (m) and the content of the thiolate groups in the molecule were changed to analyze the effect of carrier ion concentration in the bulk. In a series of potassium salt derivatives, PEO₃₅₀-SK showed the highest ionic conductivity of 6.42 × 10⁻⁵ S/cm at 50 °C. In spite of a poor degree of dissociation which was derived from the acidity of the thiolate groups, PEO _m -SM showed quite high ionic conductivity among other PEO/salt hybrids. PEO _m -SM had glass transition temperatures (T _g) 20 °C lower than other PEO/salt hybrids. Lowering the T _g was concluded to be effective in providing higher ionic conductivity for PEO-based polymer electrolytes. Received: 30 April 1999 / Accepted: 20 June 1999     

Electrochemistry and electrocatalytic activity of polypyrrole/ferrocyanide films on a glassy carbon electrode

Functionalized polypyrrole films were prepared by incorporation of Fe(CN)₆ ³⁻ as doping anion during the electropolymerization of pyrrole at a glassy carbon electrode from aqueous solution. The electrochemical behavior of the Fe(CN)₆ ³⁻/Fe(CN)₆ ⁴⁻ redox couple in polypyrrole was studied by cyclic voltammetry. An obvious surface redox reaction was observed and dependence of this reaction on the solution pH was illustrated. The electrocatalytic ability of polypyrrole film with ferrocyanide incorporated was demonstrated by oxidation of ascorbic acid at the optimized pH of 4 in a glycine buffer. The catalytic effect for mediated oxidation of ascorbic acid was 300 mV and the bimolecular rate constant determined for surface coverage of 4.5 × 10⁻⁸ M cm⁻² using rotating disk electrode voltammetry was 86 M⁻¹ s⁻¹. Furthermore, the catalytic oxidation current was linearly dependent on ascorbic acid concentration in the range 5 × 10⁻⁴–1.6 × 10⁻² M with a correlation coefficient of 0.996. The plot of i _p versus v ^1/2 confirms the diffusion nature of the peak current i _p. Received: 12 April 1999 / Accepted: 25 May 1999     

Modulation of the lower critical solution temperature of 2-Alkyl-2-oxazoline copolymers

Living cationic copolymerization of 2-isopropyl-2-oxazoline with 2-n-propyl-, 2-n-butyl-, and 2-n-nonyl-2-oxazoline results in gradient copolymers of defined composition, narrow molar mass distributions (PDI = 1.09–1.3), and defined overall degree of polymerization, set to n = 25 for all polymers. The introduction of monomer units of stronger amphiphilic character results in a systematic decrease of the lower critical solution temperature (LCST). The LCST modulation can be controlled by the choice of the comonomer as well as the comonomer ratio and was tuned in the temperature range from 46 to 9 °C. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Effect of urea on the conformational behavior of poly(N-isopropylacrylamide)

The effect of urea on the conformational behavior of poly(N-isopropylacrylamide) (PNIPAM) in dilute aqueous solution has been investigated using fluorescence spectroscopy, fluorescence quenching and fluorescence anisotropy measurements via pyrene (Py) probe and acenaphthylene (ACE) label studies. It was demonstrated that urea promotes the partitioning of the hydrophobic probe, Py, towards the bulk aqueous phase at temperatures above the lower critical solution temperature (LCST) of the polymer due to swelling of the compact coil conformation. However, the compact coil structure of the polymer at temperatures greater than its LCST is not completely destroyed, even for urea concentrations up to 3 M, at which the phase transition is hardly observed. As expected, urea has little effect on the conformational behavior of PNIPAM at temperatures below its LCST. Received: 9 February 2000/Accepted: 13 June 2000     

Synthesis and characterization of thermally reversible macroporous poly(N-isopropylacrylamide) hydrogels

Macroporous hydrogels are characterized by large pore sizes, high pore volumes, and high specific surface area. Besides these characteristics, macroporous hydrogels based on thermally reversible polymers respond to temperature changes much faster than hydrogels prepared by a conventional method. Crosslinked poly(N-isopropylacrylamide) (polyNIPAAm) forms a thermally reversible hydrogel which shows a lower critical solution temperature (LCST) ca. 33°C in aqueous solutions. We have synthesized thermally reversible polyNIPAAm hydrogels having macroporous structures by a new method. These macroporous hydrogels have large pore volumes, large average pore sizes, and faster macromolecule permeation rates in comparison to conventional polyNIPAAm hydrogels synthesized by a conventional method. Compared with conventional polyNIPAAm hydrogels, the macroporous polyNIPAAm hydrogels have higher swelling ratios at temperatures below the LCST and exhibit faster deswelling and reswelling rates. The deswelling rates are especially rapid. These thermally reversible macroporous hydrogels may be very useful in controlled active agent delivery and toxin removal, as well as dewatering of solutions. Peptides or proteins may behave as if they were in bulk solution within the large aqueous pores, and this may reduce their inactivation when such gels are used for their storage and later release. The gels may also be useful in microrobotic devices due to their fast response to temperature. © 1992 John Wiley & Sons, Inc.     

Micellization of triblock copoly(ethyleneoxide/tetrahydrofuran/ ethylene oxide)

 The association behaviour of triblock copoly(ethylene oxide/tetrahydrofuran/ethylene oxide), in particular E₁₀₀T₂₇E₁₀₀, in aqueous solutions has been investigated by means of static and dynamic light scattering, nuclear magnetic reso-nance (NMR) and surface tension techniques. On raising the polymer concentration at room temperature, the copolymer aggregates to form micelles with an aggregation number of about 105 (R _G, mic≈15 nm and R _H, mic≈13 nm, as revealed by light scattering and FT-PGSE NMR measurements, respectively). The micelles are kinetically quite stable, the micellar lifetime is shown to be more than 1 h. The residence time of a single unimer in a micelle is more than 140 ms. The apparent radius of gyration R _G, mic is fairly independent of concentration, but large effects are observed on varying the temperature. Raising the temperature initially results in an increase of the apparent micellar size, followed by a maximum at an intermediate temperature (≈45 °C). At higher temperatures a contraction of the micelles is observed. The shape of the micelles also appear to vary in this temperature interval. The interactions responsible for these phenomena are discussed in terms of, e.g., the temperature-dependent solubility of the alkylene oxide segments in water and polydispersity effects. Received: 29 January 1996 acccepted : 4 November 1996     

Development of a reference solution for the pH of seawater

A method that uses a Harned cell to perform potentiometric pH measurements has been optimized and applied to an aqueous solution of simulated seawater that contains sodium perchlorate, sodium sulfate, sodium hydrogen carbonate and boric acid and has an ionic strength I of 0.57 mol kg⁻¹. The standard metrological approach developed for the measurement of pH in low ionic strength aqueous solutions was maintained, but a few modifications were necessary, and measurement procedures and calculations were modified ad hoc from those adopted in conventional protocols. When determining the standard potential of the cell, E°, NaClO₄ salt was added to a 0.01 mol/kg HCl solution to attain the same ionic strength as the test solution and to investigate possible specific effects related to the high levels and the nature of the background electrolyte. An appropriate value of γ _±HCl (0.737) was then selected from the literature, based on a realistic value for I. Finally, in order to convert the acidity function at zero chloride molality into pH, a suitable value of γ _Cl (0.929) was calculated. As a result, we obtained pH = 8.18 (T = 25 °C) with an associated expanded uncertainty U = 0.01 (coverage factor k = 2). The aim was to establish a sound basis for the pH measurement of seawater by identifying the critical points of the experimental and theoretical procedure, and to discuss further possible developments that would be useful for achieving a reference solution.