scholarly journals INTERPOLYELECTROLYTE COMPLEXATION OF SULFONATE-CONTAINING AROMATIC POLY- AND COPOLYAMIDES IN ORGANIC AND AQUEOUS-ORGANIC MEDIA

Author(s):  
Nataliya N. Smirnova

Complex formation of sulfonate-containing aromatic poly- and copolyamides with copolymers of acrylonitrile with N,N-dimethyl-N,N-diallylammonium chloride and N,N-diethylaminoethyl methacrylate was studied in organic and aqueous-organic media. The values of conversion degree for interpolymer reactions were determined. At optimal conditions in the presence of poly-4,4'-(2-sodium sulfonate)diphenylaminoisophthalamide and  poly-4,4'-(2-sodium sulfonate)diphenylaminoterephthalamide the degree of conversion was equal to ~0.80 and 0.78, respectively. The reduction of number of sulfonate containing units in the polymer chain to 10% leads to its decrease to ~0.18.   It was shown that the nature and composition of the solvent affects the kinetics of interpolymer reactions due to the different ratio of reaggregation during the interacting of function groups in water medium with considerable force of hydrophobic interactions and in organic solvent where these forces dramatically reduce. The phase state and the composition of formed interpolyelectrolyte complexes depends on charge density along macromolecule chain of copolyamide and on the composition of the solvent used. The reduction of the number of sulfonate containing units in the macromolecule leads to polycation component increase in the complex. The formation of stoichiometric interpoly-electrolyte complexes takes place in the solvent with the same composition as that when the most significant unfolding of the polyanion chain was observed. The phase separation during the complex formation by the interpolymer reaction with copolyamide containing 5% of units with sulfonate groups or copolymer of acrylonitrile with N,N-diethylaminoethyl methacrylate is not observed.

2019 ◽  
Vol 60 (11) ◽  
pp. 40-47
Author(s):  
Natalya N. Smirnova ◽  

The interaction of sulfonate-containing aromatic poly- and copolyamides with acrylonitrile copolymers with N,N-dimethyl-N,N-diallylammonium chloride (DMDAAC) and N,N-diethylaminoethylmethacrylate (DEAEM) in organic and water-organic solutions was studied. It was shown that as a result of macromolecular reactions interpolyelectrolyte complexes (IPEC) forms. They are stabilized mainly by electrostatic forces. To characterize the interpolyelectrolyte complexes composition the φ parameter was used, that defines as the ratio of corresponding functional groups molar concentrations of interacting polyelectrolytes. The transformation degree in interpolymer reactions θ was calculated as the ratio of the salt bonds number between polyions to their maximum possible number. It was shown that the main factors determining the composition and structure of forming interpolyelectrolyte complexes are linear charge density of polyelectrolytes, the nature and composition of the solvent in which interpolymer reactions occurs. It is possible to obtain IPEC, the composition of which for the same polycation will vary from φ = 2.5 to φ = 1.0, changing these factors. It was found that at the complexation process is not accompanied by a change in the phase state of the interpolymer system, when the concentration of units with sulfonate groups in the macromolecular polyamide chain 5 mol.%. It was found that the introduction of polycation leads to the formation of IPEC structures in the form of particles with an average size of ~217.7 nm for poly-4,4'-(2-sodium sulfonate) – diphenylaminisophthalamide and ~248.1 nm in the case of poly-4,4'-(2-sodium sulfonate) -diphenylaminterephthalamide. It was shown that the decrease in the polymer content of units with sulfonate groups is accompanied by a decrease in the transformation degree from 0.65-0.66 to 0.18. It was found that the studied complexes can be transferred to the solution by increasing its ionic strength. The result obtained during this work can serve as a base for the development of for the manufacturing technology of film and membrane materials based on sulfonate-containing aromatic poly- and copolyamides.


1977 ◽  
Vol 16 (01) ◽  
pp. 30-35 ◽  
Author(s):  
N. Agha ◽  
R. B. R. Persson

SummaryGelchromatography column scanning has been used to study the fractions of 99mTc-pertechnetate, 99mTcchelate and reduced hydrolyzed 99mTc in preparations of 99mTc-EDTA(Sn) and 99mTc-DTPA(Sn). The labelling yield of 99mTc-EDTA(Sn) chelate was as high as 90—95% when 100 μmol EDTA · H4 and 0.5 (Amol SnCl2 was incubated with 10 ml 99mTceluate for 30—60 min at room temperature. The study of the influence of the pH-value on the fraction of 99mTc-EDTA shows that pH 2.8—2.9 gave the best labelling yield. In a comparative study of the labelling kinetics of 99mTc-EDTA(Sn) and 99mTc- DTPA(Sn) at different temperatures (7, 22 and 37°C), no significant influence on the reduction step was found. The rate constant for complex formation, however, increased more rapidly with increased temperature for 99mTc-DTPA(Sn). At room temperature only a few minutes was required to achieve a high labelling yield with 99mTc-DTPA(Sn) whereas about 60 min was required for 99mTc-EDTA(Sn). Comparative biokinetic studies in rabbits showed that the maximum activity in kidneys is achieved after 12 min with 99mTc-EDTA(Sn) but already after 6 min with 99mTc-DTPA(Sn). The long-term disappearance of 99mTc-DTPA(Sn) from the kidneys is about five times faster than that for 99mTc-EDTA(Sn).


2020 ◽  
Vol 11 (1) ◽  
Author(s):  
Khémesse Kital ◽  
Moumouny Traoré ◽  
Diégane Sarr ◽  
Moussa Mbaye ◽  
Mame Diabou Gaye Seye ◽  
...  

Abstract The aim of this work is to determine the thermodynamic parameters and the kinetics of complex formation between orthophthalaldehyde (OPA) and agmatine (AGM) in an alkaline medium (pH 13). Firstly, the association constant (Ka) between orthophthalaldehyde and agmatine was determined at different temperatures (between 298 K and 338 K) with a step size of 10 K. Secondly, the thermodynamic parameters such as standard enthalpy (ΔH°), standard entropy (ΔS°),and Gibbs energy (∆G) were calculated, where a positive value of ΔH° (+45.50 kJ/mol) was found, which shows that the reaction is endothermic. In addition, the low value of ΔS°(+0.24 kJ/mol) indicates a slight increase in the disorder in the reaction medium. Furthermore, the negative values of ΔG between −35.62 kJ/mol and −26.02 kJ/mol show that the complex formation process is spontaneous. Finally, the parameters of the kinetics of the reaction between OPA and AGM were determined as follows: when the initial concentration of AGM (5 × 10−6 M) is equal to that of the OPA, the results show that the reaction follows an overall 1.5 order kinetics with an initial rate of 5.1 × 10−7Mmin−1 and a half-life of 8.12 min. The partial order found in relation to the AGM is 0.8. This work shows that the excess of OPA accelerates the formation reaction of the complex.


1999 ◽  
Vol 24 (8-9) ◽  
pp. 463-470 ◽  
Author(s):  
Anja E.M. Janssen ◽  
Birte J. Sjursnes ◽  
Alexander V. Vakurov ◽  
Peter J. Halling

1980 ◽  
Vol 186 (2) ◽  
pp. 551-559 ◽  
Author(s):  
Leslie I. Gold ◽  
Edward Pearlstein

Fibronectin isolated from human plasma and from the extracellular matrices of cell monolayers mediates the attachment in vitro and spreading of trypsin-treated cells on a collagen substratum. Fibronectin-dependent kinetics of cellular attachment to collagen were studied for several adherent cell types. It was shown that trypsin-treated human umbilical-cord cells, mouse sarcoma CMT81 cells, endothelial cells, and human fibroblasts from a patient with Glanzmann's disease were completely dependent on fibronectin for their attachment to collagen, whereas guinea-pig and monkey smooth-muscle cells and chick-embryo secondary fibroblasts displayed varying degrees of dependence on fibronectin for their attachment. Radiolabelled human plasma fibronectin possessed similar affinity for collagen types I, II and III from a variety of sources. The fibronectin bound equally well to the collagens with or without prior urea treatment. However, in the fibronectin-mediated adhesion assay using PyBHK fibroblasts, a greater number of cells adhered and more spreading was observed on urea-treated collagen. Fibronectin extracted from the extracellular matrix of chick-embryo fibroblasts and that purified from human plasma demonstrated very similar kinetics of complexing to collagencoated tissue-culture dishes. Fibronectin from both sources bound to collagen in the presence of 0.05–4.0m-NaCl and over the pH range 2.6–10.6. The binding was inhibited when fibronectin was incubated with 40–80% ethylene glycol, the ionic detergents sodium dodecyl sulphate and deoxycholate, and the non-ionic detergents Nonidet P-40, Tween 80 and Triton X-100, all at a concentration of 0.1%. From these results we proposed that fibronectin–collagen complexing is mainly attributable to hydrophobic interactions.


Biochemistry ◽  
1970 ◽  
Vol 9 (20) ◽  
pp. 3894-3902 ◽  
Author(s):  
Palmer W. Taylor ◽  
Rodney William King ◽  
Arnold S. V. Burgen

1979 ◽  
Vol 32 (9) ◽  
pp. 1905 ◽  
Author(s):  
AF Godfrey ◽  
JK Beattie

The oxidation of butan-1-ol by ferricyanide ion in alkaline aqueous solution is catalysed by solutions of ruthenium trichloride hydrate. The kinetics of the reaction has been reinvestigated and the data are consistent with the rate law -d[FeIII]/dt = [Ru](2k1k2 [BuOH] [FeIII])/(2k1 [BuOH]+k2 [FeIII]) This rate law is interpreted by a mechanism involving oxidation of butanol by the catalyst (k1) followed by reoxidation of the catalyst by ferricyanide (k2). The non-linear dependence of the rate on the butanol concentration is ascribed to the rate-determining, butanol-independent reoxidation of the catalyst, rather than to the saturation of complex formation between butanol and the catalyst as previously claimed. Absolute values of the rate constants could not be determined, because some of the ruthenium precipitates from basic solution. With K3RuCl6 as the source of a homogeneous catalyst solution, estimates were obtained at 30�0�C of k1 = 191. mol-1 s-1 and k2 = 1�4 × 103 l. mol-1 s-1.


2019 ◽  
Vol 107 (2) ◽  
pp. 165-178
Author(s):  
Noura Mossaed Saleh ◽  
Ghada Adel Mahmoud ◽  
AbdelRahman AbdelMonem Dahy ◽  
Soliman Abdel-Fadeel Soliman ◽  
Refaat Mohamed Mahfouz

Abstract Kinetics of dehydration of unirradiated and γ-ray irradiated neodymium (III) acetate hydrate with 103 kGy total γ-ray dose absorbed in air atmosphere were studied by isoconversional nonisothermal method. The dehydration proceeds in two steps with the elimination of 0.8 and 0.4 mol of H2O, respectively. This result indicates that the investigated neodymium (III) acetate hydrate contains 1.2 mol of crystalline water in its structure. The dehydration reactions are best described by nucleation (A2 model) and gas diffusion (D4 model) for unirradiated and γ-ray irradiated samples, respectively. Analysis of the kinetic data using linear and nonlinear isoconversional methods showed that the apparent activation energy, Ea (kJ/mol) is dependent on the conversion degree, α, of the dehydration process. The Ea−α plots for both unirradiated and γ-ray irradiated neodymium (III) acetate hydrate showed that the dehydration is a complex process and contains multistep reactions. The results showed that γ-ray irradiation has a significant effect on the kinetics and thermodynamic parameters of the dehydration reaction. Powder X-ray diffraction showed that neodymium (III) acetate hydrate has a monoclinic system (SG P2/m) and no phase transformation was detected by γ-ray irradiation up to 103 kGy absorbed dose. The system maintains the same crystal structure before and after dehydration.


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