Anionic polymerization of ethylene oxide with cryptates as counterions: 1

A kinetic study of the anionic polymerization of ethylene oxide has been made in tetrahydrofuran at 20°C, with the cryptate K⁺ + [222] as counterion. The ion pair dissociation constant K_D has been deduced from conductivity measurements made on seeds solutions. Some ionic associations higher than cryptated ion pairs could be detected but they are negligible for living end concentrations lower than 6 × 10^?4 mol/l. k_± and k_? were determined from both sets of kinetic data obtained with and without added salt. Free alkoxide ions are one hundred times more reactive than cryptated ion pairs.     

Kinetic Study of the Photoexcited Triplet State of Free Base Porphyrins by EPR

An electron paramagnetic resonance (EPR) study of the photoexcited triplet state of four free base porphyrins is presented. The zero field splitting parameters (ZFS) |D| and |E| were calculated from the EPR spectra of the porphyrins dissolved in n-octane matrices at 80°K. |D| = 0.0359 cm^?1, |E| = 0.0079 cm^?1 for tetra phenyl porphyrin (H₂ TPP), |D| = 0.0432 cm^?1, |E| = 0.0037 cm^?1 for tetra (per-fluoro) phenyl porphyrin H₂T (per-F) PP, |D| = 0.0366 cm^?1, |E| = 0.0078 cm^?1 for tetra (para-chloro) phenyl porphyrin H₂T(P-Cl)PP, |D| = 0.0369 cm^?1, |E| = 0.0076 cm^?1 for tetra (para-methyl) phenyl porphyrin H₂T(P-Me)PP. The transient behavior of the EPR signal intensities in the last two porphyrins is discussed. The depopulation rate constants of the triplet sublevels k_p, the ratio between the population rate constants A_p (at zero field, p = x,y,z), and the spin lattice relaxation rate W within the triplet manifold, were calculated. k_x = (12 ± 2) × 10² sec^?1, k_y = (0.5 ± 0.1) × 10² sec^?1, k_z = (1.2 ± 0.4) × 10² sec^?1, A_x:A_y:A_z ? 0.63:0.01:0.33, W = (0.4 ± 0.1) × 10⁴ sec^?1 for H₂T(P-Cl)PP, k_x = (7 ± 2) × 10² sec^?1, k_y = (4 ± 1) × 10² sec^?1, k_z = (1.5 ± 0.5) × 10² sec^?1, A_x:A_y:A_z ? 0.56:0.31:0.13, W = (1.7 ± 0.4) × 10³ sec^?1 for H₂T(P-Me)PP.     

Anionic polymerization of ethylene oxide with cryptates as counterions: 2

A kinetic study of the anionic polymerization of ethylene oxide has been made in tetrahydrofuran at 20°C, with the cryptate Cs⁺ + [TC] as counterion, [TC] being a spheroidal macrotricyclic ligand. Conductance measurements have been made on THF solutions of ?₄BCs + [TC]. Ionic associations higher than cryptated ion pairs are negligible for living end concentrations lower than 3 × 10^?4 moll^?1. k_± and the alkoxide ion pair dissociation constant K_D were determined from both sets of kinetic data obtained with and without added salt knowing the value of k_? from kinetic data performed with K⁺ + [222] as counterion. Free alkoxide ions are about twenty times more reactive than cryptated caesium ion pairs.     

Kinetics measurements on a stationary disk electrode in a uniformly rotating fluid (SDERF). II. The electron transfer reaction in the Fe(CN)4−6/Fe(CN)3−6-system

The operation of the SDERF-cell in the study of the electron transfer kinetics of the Fe(CN)^4?₆/Fe(CN)^3?₆-system in 1 M KCl and 1 M KNO₃-solutions at a stationary Pt-disk electrode is reported. The experimental current—overpotential curves are recorded by linear sweep voltammetry and analysed by two different methods using the theoretical relationship derived for a stationary disk electrode placed in a free rotating fluid. Both methods give the same value for the experimental rate constant k*. The effects of the temperature (0° to 40°C) and of the ratio of the rotor radius (r_r) to the electrode radius (r_e)(r_r/r_e = 0.50 to 0.81) have been studied. The activation energy for the redox process in 1 M KCl and 1 M KNO₃ are: E_a = 3.4 ± 0.6 kcal/mol and E_a = 3.7 ± 0.7 kcal/mol respectively, while the k*-values at 25°C are: k* = (5.67 ± 0.41) × 10^?3 cm.s^?1 and k* = (4.53 ± 0.29) × 10^?3 cm.s^?1 respectively. The difference from the standard rate constant k₀ ? 0.100 cm.s^?1 is explained by the effect of the cell-geometry characterized by the G-factor, so that k° = Gk*, where G ? 19 for our cell.     

Studies on Interaction of Polysaccharide-Templated Silver Nanoparticles with Bovine Serum Albumin

In the present work, the interaction between bovine serum albumin (BSA) and as-synthesized silver nanoparticles (Oc-AgNPs) by using 4-acetamido-TEMPO-oxidized curdlan (Oc), as a reducing and stabilizing agent, was studied through fluorescence quenching method, ultraviolet visible spectrum (UV–Vis), and circular dichroism measurement. The results presented clearly indicate that the intrinsic fluorescence of BSA molecule was effectively quenched after the interaction with Oc-AgNPs by a static mechanism, which is further confirmed by UV–Vis analysis. The apparent binding constant (K), number of binding sites (n), and dissociation equilibrium constant (K_D) were calculated to be 7.5 × 10⁵ M^?1, 1.03, and 3.0 ± 0.6 μM, respectively. Furthermore, a conformational change of BSA was also observed when the Oc-AgNPs–BSA interactant formed.     

Branched-pore model applied to the adsorption of basic dyes on carbon

The branched-pore adsorption model, expressed by an external mass transfer coefficient k_f, a solid diffusivity D_s, a lumped micropore diffusion rate parameter k_b, and the fraction of macropores f, describes kinetic data from initial contact of adsorbent-adsorbate to the long-term ( > 24 hours) adsorption stages with reasonable accuracy.In this work the model is applied for three basic dye systems, namely Basic Red 22, Basic Yellow 21 and Basic Blue 69, all on carbon. A single value of each parameter describes each dye system. The k_f values are 0.18 × 10⁻²±28%, 0.3 × 10⁻²±17% and 0.2 × 10⁻² ± 20% cm s⁻¹, the D_s values are 0.33 × 10⁻⁹ 21%, 0.72 × 10⁻⁹ ± 9% and 0.72 × 10⁻⁹ ± 9% cm² s⁻¹, the k_b values are 0.65 × 10⁻⁶ ± 7.7%, 1.8 × 10⁻⁶ 0.2 × 10⁻⁶ 1% s⁻¹, while the f values are 0.55 ± 9%, 0.60 ± 10 % and 0.18 ± 11%, each for Basic Red 22, Basic Yellow 21 and Basic Blue 69 respectively.The model is based on the internal structure of the carbon particle being divided into a macropore and a micropore region. The latter has an upper-bound capacity of 241, 245 and 656 mg g⁻¹ for Basic Red 22, Basic Yellow 21 and Basic Blue 69 respectively. A sensitivity analysis for each parameter has been carried out.     

Anionic polymerization of styrene in triglyme-benzene mixtures

Living anionic polymerization of styrene was kinetically investigated in triglyme-benzene mixtures. At low concentrations of triglyme the overall propagation rate constant, k_p, was much larger than at the same concentration of monoglyme (DME) in DME-benzene mixtures. The Szwarc-Schulz plot did not have negative slopes for lithium and sodium salts at triglyme contents of 5～20vol%, and no contribution of free anions to the propagation was observed for the sodium salt. The sodium ion pair was more highly reactive than the lithium ion pair; thus at 25°C, the ion pair rate constant, k′_p, for the lithium salt was 43, 102, 135 and 165 M^?1sec^?1 at triglyme concentrations of 5, 10, 15, and 20%, respectively, while that for the sodium salt was 410, 920, and 1460 M^?1sec^?1 in 5, 10, and 15% triglyme, respectively. The dissociation constant, K, for the lithium salt was 2·4×10^?11, 1·9×10^?10 and 1·3×10^?9 M in 10, 15, and 20% triglyme, respectively and the free ion rate constant, k″_p, was 2～2·5×10⁴ M^?1sec^?1 for the lithium salt.     

Light scattering Rayleigh linewidth measurements on some globular protein solutions

An apparatus previously described for investigating the Rayleigh linewidth of light scattered from macromolecular solutions by means of the optical homodyne technique has been modified so as to obtain the autocorrelation function of the fluctuations in scattered intensity. Its operation is described and some results presented for three commercially obtainable globular proteins: chymotrypsinogen, bovine plasma albumin and urease. Measurements were made in unbuffered 0.2M NaCl aqueous solutions and the diffusion constants, D_20w, found to be 7.4±0.3×10^?7cm²s^?1, 5.8±0.1×10^?7cm²s^?1 and 3.4±0.1×10^?7cm²s^?1 respectively. There was no detectable concentration dependence. In each case the results agreed well with theoretical predictions both as regards angular variation and shape of the autocorrelation function. The effects of polydispersity are discussed.     

The Free-Radical Cleavage of the Disulfide Bond (Studied by Pulse Radiolysis)

Reaction of H atoms with glutathione leads rapidly to H + RSSR → RS · + RSH. The first observed product is RS, the spectrum of which is obtained. The spectrum of the RS?SR radical was obtained by direct attack of e^?_aq on glutathione. The rate constants of these processes were also measured. k_e?aq + RSSR = (2.7 ± 0.3) × 10⁹ M^?1 sec^?1 k_{H + RSSR} = (1.0 ± 0.2) × 10¹⁰ M^?1 sec^?1 When the OD of RS?SR is plotted vs pH a titration curve is obtained. This is due to the protonation of RS?SR with a rate constant of 2.6 × 10¹⁰ M^?1 sec^?1 which is probably followed by a cleavage to RS and RSH. In both cases the RSSHR radical cannot be detected. The spectrum attributed to the RSSHR radical is more likely to be that of RS.     

Synthesis and characterization of fluorescent PEG-polyurethane with free carboxyl groups

An innovative spherical poly(vinyl alcohol)(PVA)/peat/clay porous composite bead was prepared and shown to be suitable for use as an adsorbent. The mass transport process for the adsorption of metal ions onto this composite bead in an aqueous system was investigated. In the external mass transport process, the diffusion coefficient (D₁) of Cu⁺² and Zn⁺² ions increased with increasing initial metal ion concentration and the increasing effect was more pronounced in the initial metal ion concentrations range of 18?×?10^-3 to 22?×?10^-3?M. The diffusion rate of Zn⁺² ions was faster than that of Cu⁺² ions. In the intraparticle diffusion process, the diffusion coefficient (D₂) decreased with increasing initial metal ion concentration in the initial concentration range of 1?×?10^-3 to 4?×?10^-3?M, and the value of D₂ maintained an almost constant value in the initial concentration range of 8?×?10^-3 to 22?×?10^-3?M. The rate of ion diffusion within the adsorbent for Cu⁺² ions was faster than that for Zn⁺² ions. The adsorption mechanism was controlled by the intraparticle diffusion process. The adsorption followed the Langmuir adsorption isotherm model. The maximum amount of adsorbed metal ions for Cu⁺² and Zn⁺² ions were 22.57 and 13.62?mg/g composite bead, respectively.     

Structure and Binding of Peptide‐Dendrimer Ligands to Vitamin B12

The third‐generation peptide‐dendrimer B1 (AcES)₈(BEA)₄(K‐Amb‐Y)₂BCD‐NH₂ (B=branching (S)‐2,3‐diaminopropanoic acid, K=branching lysine, Amb=4‐aminomethyl‐benzoic acid) is the first synthetic model for cobalamin‐binding proteins and binds cobalamin strongly (K_a=5.0×10⁶ M ^?1) and rapidly (k₂=346 M ^?1 s^?1) by coordination of cobalt to the cysteine residue at the dendrimer core. A structure–activity relationship study is reported concerning the role of negative charges in binding. Substituting glutamates (E) for glutamines (Q) in the outer branches of B1 to form N3 (AcQS)₈(BQA)₄(B‐Amb‐Y)₂BCD‐NH₂ leads to stronger (K_a=12.0×10⁶ M ^?1) but slower (k₂=67 M ^?1 s^?1) cobalamin binding. CD and FTIR spectra show that the dendrimers and their cobalamin complexes exist as random‐coil structures without aggregation in solution. The hydrodynamic radii of the dendrimers determined by diffusion NMR either remains constant or slightly decreases upon binding to cobalamin; this indicates the formation of compact, presumably hydrophobically collapsed complexes.     

Proton Transfer in Liquid Ammonia Solutions Containing Water and Hydroxide Ion

The rate of proton transfer in ammonia solutions containing water and hydroxide ion was determined as a function of temperature and concentration by means of PMR spectroscopy. A first order dependence on hydroxide ion and second order dependence on water concentration was found with a rate constant of k₃ = 6.1 ± 1.2 × 10³ M^?2 sec^?1 at 25°C and ΔE^? = 4.5 ± 0.5 kcal/mole. The value of k₃ is in good agreement with that reported by other workers.     

The interaction of hydrogen sulfide with lead- and barium–cadmium–zinc-stabilized poly(vinyl chloride)

Poly(vinyl chloride) polymers stabilized with tribasic lead sulfate discolor upon exposure to hydrogen sulfide gas as a result of lead sulfide formation. The discoloration occurs for samples in both cord and sheet forms and is shown to be a function of total H₂S exposure, reaching a limiting value that is determined by the amount of lead stabilizer used in the polymer formulation. The permeation and diffusion constants for H₂S through PVC stabilized with tribasic lead sulfate and with a liquid Ba–Cd–Zn formulation are found to be P_Pb = (6.0 ± 0.2) × 10^?9, P_BaCdZn = (5.2 ± 0.2) × 10^?9 (both in cm³ gas?cm film/cm² area?sec?cm Hg), D_Pb = (1.3 ± 0.2) × 10^?7 cm²/sec, and D_BaCdZn = (6.4 ± 0.6) × 10^?8 cm²/sec, all measured at 21°C. The stabilizing efficiencies of the formulations were assessed by HCl evolution measurements, which show that exposure to H₂S decreases the initial polymer stability for both Pb-stabilized and Ba–Ca–Zn-stabilized formulations. Protection of stabilized PVC formulations from diffusing hydrogen sulfide is thus advisable for long-term stability as well as for color integrity.     

Dynamic adsorption behaviors between Cu2+ ion and water‐insoluble amphoteric starch in aqueous solutions

Dynamic adsorption behavior between Cu²⁺ ion and water‐insoluble amphoteric starch was investigated. The sorption process occurs in two stages: external mass transport occurs in the early stage and intraparticle diffusion occurs in the long‐term stage. The diffusion rate of Cu²⁺ ion in both stages is concentration dependent. In the external mass‐transport process, the diffusion coefficient (D₁) increases with increasing initial concentration in the low‐ (1 × 10^?3‐4 × 10^?3M) and high‐concentration regions (6 × 10^?3‐10 × 10^?3M). The values of adsorption activation energy (k_d1) in the low‐ and high‐concentration regions are 15.46–24.67 and ?1.80 to ?11.57 kJ/mol, respectively. In the intraparticle diffusion process, the diffusion coefficient (D₂) increases with increasing initial concentration in the low‐concentration region (1 × 10^?3‐2 × 10^?3M) and decreases with increasing initial concentration in the high‐concentration region (4 × 10^?3‐10 × 10^?3M). The k_d2 values in the low‐ and high‐concentration regions are 9.96–15.30 and ?15.53 to ?10.71 kJ/mol, respectively. These results indicate that the diffusion process is endothermic in the low‐concentration region and is exothermic in the high‐concentration region for both stages. The external mass‐transport process is more concentration dependent than the intraparticle diffusion process in the high‐concentration region, and the dependence of concentration for both processes is about equal in the low‐concentration region. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2849–2855, 2001     

Effect of acrylic acid neutralization on ‘livingness’ of poly[styrene‐ran‐(acrylic acid)] macro‐initiators for nitroxide‐mediated polymerization of styrene

BACKGROUND: The effect of acrylic acid neutralization on the degradation of alkoxyamine initiators for nitroxide‐mediated polymerization (NMP) was studied using styrene/acrylic acid and styrene/sodium acrylate random copolymers (20 mol% initial acrylate feed concentration) as macro‐initiators. The random copolymers were re‐initiated with fresh styrene in 1,4‐dioxane at 110 °C at SG1 mediator/BlocBuilder^® unimolecular initiator ratios of 5 and 10 mol%. RESULTS: The value of k_pK (k_p = propagation rate constant, K = equilibrium constant) was not significantly different for styrene/acrylic acid and styrene/sodium acrylate compositions at 110 °C (k_pK = 2.4 × 10^?6–4.6 × 10^?6 s^?1) and agreed closely with that for styrene homopolymerization at the same conditions (k_pK = 2.7 × 10^?6–3.0 × 10^?6 s^?1). All random copolymers had monomodal, narrow molecular weight distributions (polydispersity index M?_w/M?_n = 1.10–1.22) with similar number‐average molecular weights M?_n = 19.3–22.1 kg mol^?1. Re‐initiation of styrene/acrylic acid random copolymers with styrene resulted in block copolymers with broader molecular weight distributions (M?_w/M?_n = 1.37–2.04) compared to chains re‐initiated by styrene/sodium acrylate random copolymers (M?_w/M?_n = 1.33). CONCLUSIONS: Acrylic acid degradation of the alkoxyamines was prevented by neutralization of acrylic acid and allowed more SG1‐terminated chains to re‐initiate the polymerization of a second styrenic block by NMP. Copyright © 2008 Society of Chemical Industry     

Study of the mechanism of pore diffusion in batch adsorption systems

In this study the film-pore diffusion model was applied to describe system transport kinetics of three basic dye-carbon systems, namely Basic Blue 69, Basic Red 22 and Basic Yellow 21. The mass transfer parameters evaluated were the external mass transfer coefficient k_f (cm s^?1) and the effective diffusivity D_eff (cm² s^?1). A single k_f value was sufficient to describe each dye system: these were 0.15 × 10^?2, 0.20 × 10^?2 and 0.50 × 10^?2 cm s^?1 for BB69, BR22 and BY21, respectively. The effective diffusivity was found to have values much larger than those of pore diffusivities calculated from liquid diffusivities and its value decreased with increasing initial dye concentration. This was attributed to the effect of surface diffusion, hence pore diffusivity was exchanged by the effective pore diffusivity in the model. The present model was solved by the exponential curve fit technique; results were expressed in the form of experimental and theoretical Sherwood Numbers compared in terms of the residual.     

Dissociation et hydratation de nitrates alcalins dans le carbonate de propylene aqueux

Dissociation of lithium, sodium, potassium and tetraethylammonium nitrates and perchlorates in propylene carbonate has been studied by conductometry. Dissociation constants of alkali nitrates are 3·14 × 10^?3 (LiNO₃), 8·35 × 10^?3 (NaNO₃ and 1·92 × 10^?2 (KNO₃) at 25°C. The perchlorates and tetraethylammonium nitrate are strong electrolytes. The solubility products are 4·1 × 10^?4 (LiNO₃), 1·2 × 10^?5 (NaNO₃ and 2·5 × 10^?5 (KNO₃). The conductivity of saturated solutions of nitrates in the aqueous solvent has been determined up to 0·6 M water. Results are used to calculate the equilibrium constants for the reaction I^± + H₂O = I^± H₂O; Li⁺ 6·5, Na⁺ 2·5, K⁺ 0·5 and NO^?₃ 2·4. Dissociation constants, solubility products and hydration constants are compared with values reported for other solvents.     

Thermal decomposition of potassium persulfate in aqueous solution at 50°C in the presence of ethyl acrylate

Potassium persulfate modes of thermal decomposition and reactions with ethyl acrylate in aqueous solution at 50°C in nitrogen atmosphere have been investigated. It has been found that the rate of persulfate decomposition may be expressed as ?d(S₂O)/dt ∝ (S₂O)^{1.00 ± 0.06} × (M)^0.92±0.05 while the steady state rate of polymerization (R_p) is given by R_p ∝ (S₂O)^{0.50 ± 0.50} × (M)^{1.00 ± 0.06} in the concentration ranges of the persulfate, 10^?3?10^?2 (m/L), and monomer (M), 4.62?23.10 × 10^?2 (m/L), i.e., within its solubility range. In the absence of monomer, the rate of persulfate decomposition was slow and first order in persulfate at the early stages of the reaction when the pH of the solution was above 3.0. The separating polymer phase was a stable colloid at low electrolyte concentrations even in the absence of micelle generators. It has been shown that the oxidation of water soluble monomeric and oligomeric radicals by the S₂O ions in the aqueous phase, viz., \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm M}_j^ \cdot + {\rm S}_2 {\rm O}_8^{2 - } \to {\rm M}_j - {\rm O} - {\rm SO}_3^ - + {\rm SO}_4^{ \cdot - } $\end{document} is not kinetically significant in this system. It has been found that the reaction \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm M} + {\rm S}_2 {\rm O}_8^{2 - } \rightarrow{k}{\rm M} - {\rm O} - {\rm SO}_3^ - + {\rm SO}_4^{ \cdot - } $\end{document} would also lead to chain initiation at the outset of the polymerization reaction. k has been estimated as 5.41 × 10^?5 (L/m/s) at 50°C. Taking k_p as 10³ (L/m/s), k_t has been estimated as 0.168 × 10⁶ (L/m/s). The partition confficient (β) of the monomer between the polymer phase and the aqueous phase was found to be 16 ± 2, at 50°C. The rate constant for persulfate ion dissociation has been found as 1.40 × 10^?6 s^?1 at 50°C.     

Decay of the HO2 and O−2 Radicals Catalyzed by Superoxide Dismutase. A Pulse Radiolytic Investigation

The pulse radiolysis technique has been employed in the investigation of the dismutation of superoxide radicals, O^?₂ and HO₂, in the presence of superoxide dismutase in aqueous solutions. The decay of superoxide radicals in the presence of the enzyme was found to be first order in both enzyme and superoxide concentrations. An apparent second order reaction rate constant was found to be about 2 × 10⁹ M^?1 sec^?1, decreasing slightly as the pH is increased from 5 to 9.5. A mechanism which accounts for all our observations is proposed. It includes two steps: (1) formation of a product (EO^?₂ or E^?) from one enzyme (E) molecule and one O^?₂ radical ion; (2) regeneration of E by a reaction of this product with an additional O^?₂ ion radical. The reaction rate constants k = (1.4 ± 0.2) × 10⁹ and k = (1.9 ± 0.6) × 10⁹ M^?1 sec^?1 were measured at pH = 7 in an oxygenated 0.16 M sodium formate solution.     

Singlet Molecular Oxygen and Superoxide Radical Anion

Singlet molecular oxygen generated photochemically by rubrene sensitization or by direct excitation in a microwave-discharged stream of oxygen at low pressure is physically quenched by superoxide radical ion in aprotic media, with a quenching rate k_q = 3.6 ± 0.1 × 10⁷ M^?1 s^?1.