Bogdan Burczyk

Synthesis and surface properties of chemodegradable anionic surfactants: Sodium salts of sulfated 2-n-alkyl-5-hydroxymethyl-5-methyl-1,3-dioxanes

In acid-catalyzed reactions of long-chain aliphatic aldehydes (Ia-d) (a,R=n-C5H11; b,R=n-C7H15; c,R=n-C9H19; d,R=n-C11H23) with 1,1,1-tris(hydroxymethyl)-ethane (II), 2-n-alkyl-5-hydroxymethyl-5-methyl-1,3-dioxanes (IIIa-d) were obtained. Then they were reacted with SO3·pyridine complex in dry carbon tetrachloride solution, to obtain trisubstituted derivatives of 1,3-dioxane (IVa-d). They constitute a new group of chemodegradable, acetal-type anionic surfactants, which may readily hydrolyze and oxidize to nonsurfactant compounds. Physical data of the new compounds and some surface properties, such as Krafft point, critical micelle concentration (CMC), surface tension of aqueous solution near CMC (γCMC) and wetting and foaming properties, were determined. Sodium salts of sulfated 2-n-alkyl-5-hydroxymethyl-5-methyl-1,3-dioxanes (IVa-d) exhibit aqueous solution properties similar to those of the well-known sodium alkyloligooxyethylene sulfates. Presence of the 5-methyl-1,3-dioxane moiety in molecules of compounds IVa-d introduces hydrophobic character comparable to the effect of three oxyethylene groups (-CH2CH2O-) or of two methylene groups (-CH2-) of the alkyl chain in sodium alkyl ether sulfates [R(OCH2CH2)mOSO3Na] with equal R value.

Synthesis and hydrolysis of chemodegradable cationic surfactants containing the 1,3-dioxolane moiety

In acid-catalyzed reactions of long-chain aliphatic aldehydes (Ia-d wherea=n-C7H15;b=n-C9H19;c=n-C11H23; d=n-C13H27), and tridecan-7-on (Ie) with 3-chloro-1,2-propane-diol, 2-alkyl- and 2,2-dihexyl-4-chloromethyl-1,3-dioxolanes (IIa-e) were obtained. They were reacted with anhydrous dimethylamine to obtain, respectively, 2-alkyl-and [(2,2-dihexyl-1,3-dioxolan-4-yl)methyl] dimethylamines (IIIa-e), which were quaternized with methyl bromide to obtain the desired ammonium bromides (IVa-e). The structure and purity of the compounds was proved by mass spectrometry and proton nuclear magnetic resonance spectroscopy. Additionally, [(2-methyl-1,3-dioxolan-4-yl)methyl] trimethylammonium bromide and [(2,2-dimethyl-1,3-dioxolan-4-yl)-methyl] trimethylammonium bromide were synthesized as nonaggregating standards. Hydrolysis reactions of the synthesized ammonium bromides were performed by 0.1 M hydrochloric acid in 1∶1 (vol/vol) 1,4-dioxane-water mixtures at 50, 60 and 70°C. Rate constants of hydrolysis reactions were determined by observing carbonyl group formation at 280 nm. The hydrolytic reactivity of the studied surfactants (IVa-c,e) was determined under unaggregated conditions. Compound IVd showed decreased reactivity. The length of the 2-alkyl group has a minor effect on rate constant values. The influence of various substituents at the C-4 atom of the 2-nonyl-1,3-dioxolan-4-yl derivatives on rate constants was also investigated.

Chemical structure and surface activity: VIII. Statistical evaluation of the influence of alkyl monoethers of polyoxyethylene glycols structure on their adsorption at the aqueous solution-air interface

In a reaction of bis(2-hydroxyethyl)disulphide with methyl- or ethyloxirane (proylene or α-butylene oxide) carried out in the presence of ternary amine as catalyst, hydrophobic oligomers were obtained. By reacting them with oxirane (ethylene oxide), surface active block copolymers were obtained. The all-block copolymers were characterized and their efficiency of adsorption as well as foaming and wetting properties were measured

Synthesis and surface properties of oxyethylenated 2-alkyl-5-hydroxymethyl-5-ethyl-1,3-dioxanes

In acid-catalyzed reactions of long chain aliphatic aldehydes (I) (R=n−C7H15; n−C9H19; n−C11H23) with 1,1,1-tris(hydroxymethyl)propane (II), 2-alkyl-5-hydroxymethyl-5-ethyl-1,3-dioxanes (III) were obtained. The latter were then reacted with ethylene oxide in the presence of sodium methoxide.Three series of oxyethylenated cyclic acetal derivatives (IV) were obtained. They constitute a new group of chemodegradable surfactants which readily hydrolyze and oxidize in natural water reservoirs. Physical data of the new compounds and some surface properties such as cloud points (Cp), critical micelle concentrations (cmc), changes of free energy of micellization, (ΔG°cmc), surface tensions of aqueous solutions near cmc, γmin, and wetting and foaming properties, were determined. The surfactants (IV) have aqueous solution properties similar to those of oxyethylenated longchain aliphatic alcohols. It is shown that the micellization of surfactants (IV), expressed in terms of ΔG°cmc, depends both on the length of the aliphatic chain at the C-2 carbon atom and on the presence of ethyl group at C-5 of 1,3-dioxane ring which enhances the hydrophobic character of derivatives (III). Hence, the surfactants have a higher surface activity than oxyethylenated 2-alkyl-4-hydroxymethyl-1,3-dioxolanes or 2-alkyl-5,5-bis-(hydroxymethyl)-1,3-dioxanes. The use of 2-alkyl-5-hydroxymethyl-5-ethyl-1,3-dioxanes (III) in surfactant synthesis is an example of applying hydrophobic intermediates obtained from aldehydes only. This, and the chemodegradability mentioned make the compounds a very interesting group of new surfactants.

Surface activity and micelle formation of chemodegradable cationic surfactants containing the 1,3-dioxolane moiety☆

Abstract Systematic studies of adsorption phenomena and micellization for several cationic acetal-type surfactants: [(2-alkyl-1,3-dioxolane-4-yl)methyl]trimethylammonium bromides (C n -D-TAB; where C n C 9 H 19 , C 11 H 23 or C 13 H 27 ) and [(2,2-dialkyl-1,3-dioxolane-4-yl)methyl]trimethylammonium bromides (C n C m -D-TAB; where C n C 8 H 17 or C 13 H 21 and C m CH 3 , or C n C m C 6 H 13 ) have been carried out using surface tension measurements. Because these surfactants contain a 1,3-dioxolane moiety (D), they can be applied as a new acid-hydrolyzable type of chemodegradable surfactant. The structural effects of both the alkyl substituents (structural isomerism), and the 1,3-dioxolane ring on the adsorption (i.e. on the surface excess concentration, the area per molecule at the surface, the standard free energy of adsorption) and the micellization parameters have been discussed and compared with respect to parameters of the “classical” alkyltrimethylammonium bromides (C n -TAB) and alkyl trimethylammonium bromides containing oxythylene (EO 1 ) and dioxyethylene (EO 2 ) units (C n -EO 1 -TAB and C n -EO 2 TAB, respectively) also. The C n -D-TAB surfactants exhibit micellar properties similar to those of C n -EO 2 -TAB. The values of the standard free energy contribution of the 1,3-dioxolane ring [-D-] in the C n -D-TAB derivatives to the micellization and the adsorption processes ( ΔG mic °[-D-] = −5.7 kJ mol −1 and ΔG ads °[-D-] = −21.5 kJ mol −1 , respectively) showed that the [-D-] moiety is approximately 1.7 times more hydrophobic than the methylene group of the alkyl chain in promoting micellization ( ΔG mic °[CH 2 ] = −3.5 kJ mol −1 ) and 6.3 times more effective in promoting adsorption ( ΔG ads °[CH 2 ] = −3.35 kJ mol −1 ). The difference ΔΔG °[-D-]( = ΔG ads °[-D-] − ΔG mic °[-D-] = −16 kJ mol −1 ) indicates a higher strength of adsorption of the five-membered 1,3-dioxolane ring at the infinite dilution surface film than the tendency to micellization.

Surfactin Isoforms from Bacillus coagulans

Abstract Bacillus coagulans has been found to produce several surfactins that are powerful lipopeptide surfactants. Four main components with molecular weights 1007, 1021 and 1035 Da were separated. Their structures have been confirmed by spectrometric and spectroscopic studies and by acid hydrolysis. The compounds were found to represent two pairs of surfactin isoforms in which β-hydroxy-iso-C14 or anteiso-C15 fatty acids are linked to the [Leu7] or [Val7] heptapeptide moiety by both an amide group and a lactone bond.

An Efficient Method for the Preparation of Pure Long-Chain CIS-and Trans-2-n-Alkyl-5-Hydroxy-1,3-Dioxanes #

Abstract The title compounds were obtained with high yields from four-component mixtures of glycerol acetals by combining the transacetalization reaction with the crystallization process followed by fractional distillation. Part XXII in the series: Acetals and Ethers. For Part XXI see Ref. 1

Micellar degree of dissociation of hydroxyfunctionalized quaternary ammonium bromides

Abstract The micellar degrees of dissociation, α, of the hydroxyfunctionalized quaternary ammonium bromides having the structures: [RN + (CH 3 ) 2 R 1 ]Br − where R = C 16 H 33 , R 1 = CH 2 CH 2 OH (1a) R = C 16 H 33 , R 1 = CH 2 CH(CH 3 )OH (1b) R = C 16 H 33 , R 1 = CH 2 CH(C 2 H 5 )OH (1c) R = C 14 H 29 CH(OH)CH 2 , R 1 = CH 3 (2) have been determined at 25°C by measurements of the added salt effects on their critical micelle concentration, ion selective potentiometry and electric conductivity. The α values steadily increase as the length of R 1 increases in the surfactant molecule. The presence of the hydroxy group, i.e., its nature and position, does not introduce noticeable effects on the α values.

Acetals and ethers. XV. Reactivity of mono- and disubstituted cyclic acetals toward ozone in aqueous solution

Mono- and disubstituted derivatives of 1,3-dioxolane and 1,3-dioxane were oxidized by ozone in aqueous solutions containing monosodium carbonate. In both alkylsubstituted 1,3-dioxacyclane series the rates of oxidation increase with increasing length of alkyl substituents at the C-2 dioxacyclane carbon atom. However, the alkyl derivatives of 1,3-dioxane (III, IV, V) are more resistant toward ozone than the respective 1,3-dioxolane derivatives (I, II). The pseudo-first order rate constants for the oxidation of glycerol acetals (VIIa–VIId) decrease in the order:cis-dioxolane>trans-dioxolane>cis-dioxane>trans-dioxane.

Antimicrobial activity and biodegradability of N -alkylaldonamides

A number of N-alkylaldo-namides, i.e., nonionic saccharide-based surfactants such as N-alkyl-N-methylgluconamides, N-alkyl-N-methyllactobionamides and N-alkyl-N,N’-bis[(3-D-aldonamidopro-pyl]amines were evaluated for environmental responses. All the N-alkylaldonamides were screened for antimicrobial activity against selected gram-positive (Staphylococcus aureus PCM 1944, Sarcina lutea PCM 1947, Bacillus subtilis PCM 1949, gram-negative (Escherichia coli PCM 2057, Serratia marcescens PCM 549, Pseudomonas putida PCM 2124) bacterial strains and some fungi (Saccharomyces cerevisiae, Penicillum citrinum, Aspergillus niger). It was generally recognized that the compounds tested were completely inactive towards fungi. N-Alkyl-N-methylgluconamides and N-alkyl-N-methyllactobionamides were practically inactive towards the bacteria studied. On the other hand, dicephalic saccharide-based surfactants were active against gram-positive cocci, much more strongly than the N-alkyl-N-methylaldonamides. Using the closed-bottle test (OECD guideline 301D), the biodegradability of these surfactants was determined. N-Alkyl-N-methyl-aldonamides may be considered to be readily biodegradable by activated sludge. The dicephalic surfactants studied showed slower biodegradation rates and they may be considered to be inherently biodegradable. Members of this class of saccharide surfactants exibit biological properties needed for environmental acceptance.