The Effect of Surfactants on the Acid-Base Behaviour of Methyl Red. Part II. A Spectrophotometric Comparison of the Effect of Triton X-100 and β-Cyclodextrin

1994 ◽  
Vol 59 (2) ◽  
pp. 322-329
Author(s):  
Jana Jirasová ◽  
Jiří Bílý ◽  
Ludmila Čermáková

The effect of the non-ionogenic surfactant Triton X-100 (TX) and β-cyclodextrin (CD) on the absorption bands of methyl red was examined. The interactions of methyl red with the both substances were studied based on changes in the absorption curves after their resolution into Gaussian bands. The conditional dissociation constants of methyl red were determined at various concentrations of the additives (in the case of TX, both below and above its cmc value). At cTX = 0.06 mol l-1 the change in the conditional dissociation constant of methyl red was ∆pKa = -0.58 and at cCD = 6 mmol l-1 the ∆pKa value was identical.

1990 ◽  
Vol 55 (6) ◽  
pp. 1491-1499 ◽  
Author(s):  
Jana Jirasová ◽  
Jiří Bílý ◽  
Ludmila Čermáková

The effect of a cationic (CPB) and an anionic (SDS) surfactant on the bands in the absorption spectra of methyl red was studied. The interactions of methyl red with the two surfactants were monitored on the basis of the changes in the absorption curves that were mathematically deconvoluted into Gaussian shape absorption bands. The methyl red dissociation constants were determined in the presence of the two surfactants at sub- and supercritical micelle concentrations. The methyl red conditional dissociation constants changed by ΔpKa = -1.47 for c(CPB) = 5 mmol l-1 and ΔpKa = 0.81 for c(SDS) = 4 mmol l-1. The contributions of the individual forms of methyl red to the interactions with CPB and SDS were discussed.


2008 ◽  
Vol 12 (02) ◽  
pp. 75-84
Author(s):  
Tatyana N. Kropacheva ◽  
Richard N. S. van der Haas ◽  
Robert van der Steen ◽  
Peter Gast ◽  
Hans J. Schuitmaker ◽  
...  

The binding and acid-base equilibria of the two novel mesoporphyrin derivatives, PB07 and PB109 (quino[4,4a,5,6-efg]- annulated 7-demethyl-8-deethylmesoporphyrin and 2'-cyano-8'-formyl-N'-methyl-1',1a',5a',6'-tetrahydroacrido [4,5,5a,6-bcd]- annulated 2,3-dihydromesoporphyrin, resp.), which are promising agents for photodynamic therapy (PDT), were studied in aqueous solutions of different surfactants (Triton X-100 (TX-100), dodecyl maltoside (DDM), cetyltrimethylammonium bromide (CTAB), lithium dodecyl sulfate (LDS)) and phosphatidyl choline (PC) liposomes. In all cases, the porphyrins are solubilized at neutral/alkaline pH in monomeric form and remain micelle/liposome-bound independently of their ionization state. The dissociation constants of the solubilized porphyrins are found to be influenced by the charge of the surface groups of the carrier. The protonation of pyrrole/quinoline nitrogens of the studied porphyrins is facilitated in the following order: LDS ≫TX-100 (DDM, PC liposomes) > CTAB. The dissociation constants of PB 07 carboxylic groups are similar in neutral/cationic micellar and liposome solutions and are significantly decreased for LDS-bound pigment. The results provide necessary information for the optimization of delivery systems for PB 07 and PB 109 when applied as sensitizers in PDT.


1983 ◽  
Vol 48 (5) ◽  
pp. 1290-1304 ◽  
Author(s):  
Josef Havel ◽  
Irena Burešová-jančářová ◽  
Vlastimil Kubáň

The effect of cationic surface-active substances - tensides - on the acid-base and optical properties of anionic organic analytical reagents was studied by spectrophotometric methods on the example of bromocresol green with Septonex in the submicelle and micelle tenside concentration regions. The acid-base properties of bromocresol green under the given experimental conditions depend on the concentrations of the tenside and reagent and on the type and concentration of the inert electrolyte. Changes in the conditional dissociation constant of the reagent were quantitatively described by equations that were derived from the relationships for the dissociation constant of the acid-base transition of the reagent LH/L-, the equilibrium constant for formation of the stoichiometric ion-associates between the tenside T+ and the anionic acid-base form of the reagent L- or the anion of the inert electrolyte X- and the equilibrium constant for formation of the polymeric micelle aggregates (T+)n. The experimental values of the conditional dissociation constants for bromocresol green for various tenside or inert electrolyte concentrations are in good agreement with these theoretically derived relationships.


1987 ◽  
Vol 52 (10) ◽  
pp. 2401-2411 ◽  
Author(s):  
Jitka Jurasová ◽  
Vlastimil Kubáň

Changes in the optical and acid-base characteristics of neutral red in the presence of hexadecylpyridinium bromide, hexadecyltrimethylammonium bromide, α-carbethoxypentadecyltrimethylammonium bromide (Septonex), sodium dodecyl sulphate, Triton X-100, and BRIJ 35 in submicellar and micellar concentrations were studied spectrophotometrically. The conditional dissociation constant of neutral red pKai* depends on the kind and concentration of tenside, kind and concentration of inert electrolyte, and concentration of the cationic dye. Changes in the pKai* values are described in terms of formation of ionic associates of the dye with the tenside and of the inert electrolyte ions with the tenside. The validity of equations for the dependence of pKai* on the logarithm of tenside concentration was proved experimentally over a wide region of cationic tenside concentrations. The changes in pKai* can also be partly accounted for by changes in the nature of the solvent. A titrimetric method based on the changes in the conditional dissociation constant of neutral red is suggested for the determination of tensides in aqueous solutions using photometric end point indication.


1982 ◽  
Vol 47 (11) ◽  
pp. 2882-2889
Author(s):  
Nadezhda Likhareva ◽  
Ladislav Šůcha ◽  
Miloslav Suchánek

Two new compounds from the formazan series, viz. 1,3-diphenyl-5-(1H-tetrazol-2-yl)formazan and 1,3-diphenyl-5-(2H-1,2,4-triazol-3-yl)formazan, were prepared, and the dissociation constants and molar absorptivities of all of their acid-base species were determined spectrophotometrically employing the SPEKTFOT computer program.


1982 ◽  
Vol 47 (10) ◽  
pp. 2676-2691 ◽  
Author(s):  
Miroslav Macka ◽  
Vlastimil Kubáň

The optical and acid-base characteristics of BrPADAP and ClPADAP were studied in mixed water-ethanol and water-DMF media and in 10% ethanol medium in the presence of cationic, anionic and nonionic tensides. The composition, optical characteristics, molar absorption coefficients and equilibrium constants of the ML and ML2 complexes with zinc(II) ions were found by graphical analysis and numerical interpretation of the absorbance curves by the modified SQUAD-G program. Optimal conditions were found for the spectrophotometric determination of Zn(II) in the presence of 0.1% Triton X-100 or 1% Brij 35 in alkaline media with pH = 6.5-10. BrPADAP and ClPADAP are the most sensitive reagents (ε = 1.3-1.6 . 105 mmol-1 cm2 at 557 and 560 nm, respectively) for the determination of zinc with high colour contrast of the reaction (Δλ = 104 nm) and selectivity similar to that for the other N-heterocyclic azodyes (PAN, PAR, etc.).


1981 ◽  
Vol 46 (5) ◽  
pp. 1090-1106 ◽  
Author(s):  
Irena Burešová ◽  
Vlastimil Kubáň ◽  
Lumír Sommer

The acid-base and optical properties of Chromazurol S and Eriochromazurol B in the presence of 1 . 10-6 - 2 . 10-2M solutions of cetylpyridinium bromide, cetyltrimethylammonium bromide and 1-ethoxycarbonylpentadecyltrimethylammonium bromide (Septonex) and 0.001-1.0% w/v solutions of octylphenolpolyethylene glycol ether (Triton X-100), polyoxyethylenemonolauryl ether (Brij 35) and lauryl sulphate sodium salt were determined by graphical and numerical interpretation of absorbance curves. The poorly soluble ion associates, which can be extracted into chloroform and which have the defined composition [LH4-nn-.n T+] or [LH3-nn-.n T+] are formed at submicellar concentration of the tenside. In regions close to the critical micellar concentration of the tenside, soluble binary complexes of the acid-base forms of the reagent are formed with tenside micelles. The conditional stability constants of the reagent acid-base equilibrium depend on the type and concentration of the tenside, on the reagent concentration, on the concentration and type of inorganic acid anions and on the ionic strength of the solution. The mechanism of interaction of the reagent with the tenside and the probable structure of the binary species are discussed.


2001 ◽  
Vol 91 (3) ◽  
pp. 1364-1371 ◽  
Author(s):  
Peter D. Constable

The strong ion approach provides a quantitative physicochemical method for describing the mechanism for an acid-base disturbance. The approach requires species-specific values for the total concentration of plasma nonvolatile buffers (Atot) and the effective dissociation constant for plasma nonvolatile buffers ( K a), but these values have not been determined for human plasma. Accordingly, the purpose of this study was to calculate accurate Atot and K a values using data obtained from in vitro strong ion titration and CO2tonometry. The calculated values for Atot (24.1 mmol/l) and K a (1.05 × 10−7) were significantly ( P < 0.05) different from the experimentally determined values for horse plasma and differed from the empirically assumed values for human plasma (Atot = 19.0 meq/l and K a = 3.0 × 10−7). The derivatives of pH with respect to the three independent variables [strong ion difference (SID), Pco 2, and Atot] of the strong ion approach were calculated as follows: [Formula: see text] [Formula: see text], [Formula: see text]where S is solubility of CO2 in plasma. The derivatives provide a useful method for calculating the effect of independent changes in SID+, Pco 2, and Atot on plasma pH. The calculated values for Atot and K a should facilitate application of the strong ion approach to acid-base disturbances in humans.


2019 ◽  
Vol 16 (31) ◽  
pp. 755-764
Author(s):  
Roberto FERNANDEZ-MAESTRE ◽  
Alonso J MARRUGO-GONZÁLEZ

Chalcones (α,β-unsaturated ketones) containing aromatic or heterocyclic radicals are highly reactive, allowing the synthesis of novel organic compounds. In this study, the dissociation constants (pKa) of seven chalcones derived from 8-hydroxyquinoline were determined and the influence on dissociation of substituents in the phenyl group (-CH3, -OCH3, -N(CH3)2, -Cl, -Br, and -NO2) was analysed. pKa values are important because they determine the pH at which ligands are fully deprotonated -when they show their maximum chelating properties- and determine the ligands interactions at different pH values. The chalcones’ pKa’s were calculated by visible ultraviolet spectroscopy in a water-ethanol (1:1) mixture using the Henderson-Hasselbach equation. It was shown that the 8-hydroxyquinolinic fragment has a large electron donor effect on the π system of the chalcones. The introduction of substituents (R) in the phenyl fragment of the chalcones slightly affected the dissociation of the hydroxyl group and the protonation of the nitrogen in the hydroxyquinoline fragment. The acceptor substituents (Cl, Br, NO2) increased the polarity of OH- and its acidity. Nitrogen protonation decreased electron donor properties of this fragment, and deprotonation of the hydroxyl caused the opposite effect. Substituents introduction in the phenyl fragment slightly affected hydroxyl group dissociation and nitrogen protonation.


2009 ◽  
Vol 6 (8) ◽  
pp. 1539-1561 ◽  
Author(s):  
A. F. Hofmann ◽  
J. J. Middelburg ◽  
K. Soetaert ◽  
F. J. R. Meysman

Abstract. A new pH modelling approach is presented that explicitly quantifies the influence of biogeochemical processes on proton cycling and pH in an aquatic ecosystem, and which accounts for time variable acid-base dissociation constants. As a case study, the method is applied to investigate proton cycling and long-term pH trends in the Scheldt estuary (SW Netherlands, N Belgium). This analysis identifies the dominant biogeochemical processes involved in proton cycling in this heterotrophic, turbid estuary. Furthermore, information on the factors controlling the longitudinal pH profile along the estuary as well as long-term pH changes are obtained. Proton production by nitrification is identified as the principal biological process governing the pH. Its acidifying effect is mainly counteracted by proton consumption due to CO2 degassing. Overall, CO2 degassing generates the largest proton turnover in the whole estuary on a yearly basis. The main driver of long-term changes in the mean estuarine pH over the period 2001 to 2004 is the decreasing freshwater flow, which influences the pH directly via a decreasing supply of dissolved inorganic carbon and alkalinity, and also indirectly, via decreasing ammonia loadings and lower nitrification rates.


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