Bifunctional N-Oxides of Alkyldiamidoamines

A homologous series of new surface-active 1,1-bis{[3-(N,N-dimethylamino)ethyl]-amido}alkane-di-N-oxides were synthesized in the reaction of an appropriate diethyl 2-alkylmalonate with N,N-dimethylethylenediamine followed by oxidation with an aqueous solution of hydrogen peroxide. The adsorption isotherms of their aqueous solutions were measured and evaluated to obtain adsorption parameters: critical micelle concentration (CMC), surface excess concentration (Γ_CMC), equilibrium surface tension at the CMC (γ _CMC), cross-sectional area of the adsorbed surfactant molecule (A _CMC), standard free energies of adsorption and micellization

Synthesis and Properties of 1,1-bis{[3-(<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-Dimethylamino)propyl]amido}alkane-di-<Emphasis Type="Italic">N</Emphasis>-oxides

A homologous series of new surface-active 1,1-bis{[3-(N,N-dimethylamino)propyl]amido}alkane-di-N-oxides were synthesized in the reaction of an appropriate diethyl 2-alkylmalonate with N,N-dimethylamino-1,3-propanediamine followed by oxidation with aqueous hydrogen peroxide. The adsorption isotherms of their aqueous solutions were measured and evaluated to obtain adsorption parameters: critical micelle concentration (CMC), surface excess concentration (Γ_CMC), equilibrium surface tension at the CMC (γ_CMC), cross-sectional area of the adsorbed surfactant molecule (A _CMC), efficiency of surface adsorption (pC₂₀), standard free energies of adsorption (ΔG°_ads), and micellization (ΔG°_CMC). All investigated di-amidoamines and di-N-oxides were practically non-toxic to selected bacteria and yeasts. These compounds are readily biodegradable in the Closed Bottle Test inoculated with activated sludge. Surface and biological properties showed that this group of N-oxide-type compounds has high surface activity and fulfills requirements for environmental acceptance.

Synthesis and Surface Properties of Dicephalic Surfactants with a 1,3-Dioxane Ring

A new group of surface active dicephalic derivatives of 1,3-dioxane, i.e., 2-alkyl-5,5-bis{[3-(N,N-dimethylamino)propyl]amido}-1,3-dioxane-di-N-oxides, were synthesized with high yields by the reaction of an appropriate 2-alkyl-5,5-bis-(carboxyethyl)-1,3-dioxane with an excess of N,N-dimethyl-1,3-propanediamine followed by oxidation with an aqueous solution of hydrogen peroxide. Structures and purity of all intermediates and final di-N-oxides were confirmed by means of ¹H-NMR and ESI-MS spectroscopy. Synthesized compounds showed high surface activity with low values of critical micelle concentration and high effectiveness of surface tension reduction (γ _CMC). However, only derivative with the longest 2-alkyl substituent showed good foaming and moderate emulsifying properties.

Synthesis of Sulfated Sodium Salts of 1-Alkylamino-3-alkyloxy-2-propanols and N,N-Di-(2-hydroxy-3-alkyloxy propyl) Alkylamines as Potential Surfactants

1-Alkylamino-3-alkyloxy-2-propanols, V (a–g) and N,N-di-(2-hydroxy-3-alkyloxy propyl) alkylamines, VI (a–g) were prepared with the same chain length both for alkyl amino and alkyloxy groups by condensation of alkyl glycidyl ethers with long chain alkylamines by employing thermal and microwave-assisted methods. All the products were characterized by ¹H-NMR, IR and fast atom bombardment mass spectrometry studies. These compounds were further sulfated and evaluated as their sodium salts for surfactant properties namely surface tension, critical micelle concentration, emulsifying property, wetting, foaming power and calcium tolerance. Sulfated 1-dodecylamino-3-dodecyloxy-2-propanol, VII c and sulfated N,N-di-(2-hydroxy-3-dodecyloxy propyl) dodecylamine, VIII c were found to exhibit superior surfactant properties among the respective series of monomers and dimers.

Synthesis and Properties of Functionalized Alkylaldonamides

Application studies of novel saccharide-type nonionic surfactants were performed. The homolog series of N-alkyl-N-(2-hydroxyethyl)gluconamides and N-alkyl-N-(2-hydroxyethyl)glucoheptonamides (alkyl: n-C₁₀H₂₁, n-C₁₂H₂₅, and n-C₁₄H₂₉) were synthesized and their structures were confirmed by means of elemental analysis and ¹H-NMR spectroscopy. The investigations showed that the application of N-alkyl-N-(2-hydroxyethyl)aldonamides as surfactants in an aqueous media can be limited. This is because of their relatively high Krafft point temperature. However, some variants can be successfully applied in mixtures with an anionic surfactant: sodium salt of n-dodecyl sulfate (SDS). The addition of SDS causes significant improvement of the Krafft point temperatures. In some cases a synergistic effect was observed, i.e., the Krafft point temperature of the binary mixture was lower that the corresponding values for the solutions containing individual compounds. It is also remarkable, that the aqueous solutions of binary surfactant mixtures were characterized by improved foaming properties, as compared to that of pure SDS.

Synthesis and Properties of Surface Chemically Pure Alkylamidoamine-N-oxides at the Air/Water Interface

A homologous series of surface active 2-(alkanoylamino)ethyldimethylamine-N-oxides, EDA-p(O), and 3-(alkanoylamino)propyldimethylamine-N-oxides, PDA-p(O), were synthesized. Their aqueous stock solutions were processed by the automatically operating apparatus to remove surface-active contamination and provide chemical purity at the air/water interface. In case of 3-(tetradecanoylamino)propyldimethylamine-N-oxide, PDA-14(O), the difference between equilibrium surface tension values of the purified surfactant solutions and the corresponding values of the solutions prepared from the “as received” compounds amounts to 15 mN m⁻¹. Moreover, in presence of the surface-active contaminants time needed to reach equilibrium surface tension values is over 2 h. For the solution of the “surface-chemically pure” grade the change of the surface tension within adsorption time is negligible and the equilibrium is reached instantaneously. Physicochemical properties of obtained surface-chemically pure aqueous solutions of N-oxides of alkylamidoamines and adsorption parameters (standard free energy of adsorption, ΔG°_ads, surface excess by saturation surface concentration, Γ_∞, minimum surface area demand per molecule adsorbed, A _min) were evaluated from the equilibrium surface tension versus concentration isotherms at the air/water interface using Gibbs’s equation. The introduction of the CH₂ moiety into the intermediate part of molecule causes a slight decrease of the hydrophobic character of surfactant. Also the minimum surface area demand, A _min, is slightly greater for PDA series than for the corresponding EDA derivatives. Surface potential measurements were performed in addition to surface tension studies. Electric surface potential versus concentration isotherms was determined. Surface potential increases with increasing surfactant’s bulk concentration for all investigated compounds. At highest concentrations, where interface is almost saturated, changes of surface potential become almost negligible.

Effects of Pin-up Oxygen on [60]Fullerene for Enhanced Antioxidant Activity

The introduction of pin-up oxygen on C₆₀, such as in the oxidized fullerenes C₆₀O and C₆₀O_n, induced noticeable increase in the antioxidant activity as compared to pristine C₆₀. The water-soluble inclusion complexes of fullerenes C₆₀O and C₆₀O_n reacted with linoleic acid peroxyl radical 1.7 and 2.4 times faster, respectively.

Preparation,Surface-Active Properties and Antimicrobial Activities of Bis(Ester Quaternary Ammonium) Salts

New cationic surfactants, bis-quaternary ammonium salts, were prepared from N,N-dimethylaminoalkyl esters of saturated fatty acids and products of the reactions of epichlorohydrin with primary amines: pentyl-, hexyl- and octylamine. The bis (ester–ammonium) salts obtained were examined in respect to their surface-active properties: critical micelle concentration (CMC), effectiveness of surface tension reduction (γ_CMC), and adsorption efficiency (pC₂₀). All these surfactants showed good water solubility and low critical micelle concentrations of more than two orders of magnitude lower than these of corresponding mono-alkylammonium salts. They also showed good wetting capability, but worse foaming properties. All the surfactants tested were nontoxic to gram-negative bacteria, but some of them inhibited the growth of gram-positive bacteria and yeast.

Influence of Sodium Ions on Micelles of Surfactin-C16 in Solution

The properties of surfactin-C₁₆ aqueous solution in the presence of Na⁺ ions, produced by Bacillus subtilis, were studied by the fluorescence method. The critical micelle concentration (CMC) of surfactin-C₁₆ was measured as 24.7 μM in 0.05 M Tris buffer (pH 8.5–8.6). With an increase in Na⁺ concentration, the CMC value and micropolarity of surfactin-C₁₆ decreased while the microviscosity increased, which means that the addition of Na⁺ improves the surface activity and enhances the micellization of the surfactin-C₁₆ in solution. The preliminary aggregation number (N) was obtained by the steady-state fluorescence method.

Preparation and Application of Fluorinated Cationic Surfactants

Four fluorinated cationic surfactants were prepared by condensing 2,2,3,3, tetrafluoro-1-propyl chloroacetate with stoichiometric amounts of pyridine, 2-hydroxypyridine, 8-hydroxyquinoline and 8-hydroxyquinaldine to produce four quaternary ammonium salts. The surface and biocidal properties of these surfactants were investigated. Surface properties of their solutions including surface tension, critical micelle concentration (CMC), effectiveness (Π_cmc), maximum surface excess (Γ_max) and minimum surface area (A _min) were investigated with respect to different concentrations at 25 °C. Standard free energies of micellization and adsorption of the prepared surfactants in the aqueous solution were studied. The biocidal activity was determined via the inhibition zone diameter of prepared compounds which tested against six strains as a representative group of microorganisms.

Synthesis of Ethyl 5 Z ,9 Z ,12 Z -octadecatrienoate (ethyl pinolenate) and Methyl 12 Z ,15 Z -octadecadienoate

Pinolenic acid (5Z,9Z,12Z-octadecatrienoic acid, 1a), one of the most abundant trienoic fatty acids in nature, is very difficult to obtain in quantity in a pure state from the highly complex mixture of unsaturated tall oil fatty acids. For this reason its chemistry has been little studied when compared to linolenic or linoleic acids. A simple synthesis of esters of 1a and of 12Z,15Z-octadecadienoic acid 3 using the one pot double Wittig procedure is described here. The products of double Wittig reactions were purified by argentation chromatography, and their structural purity was established by ¹H-, ¹³C-NMR and 2D-NMR spectroscopies.

Overexpression of a FAD3 Desaturase Increases Synthesis of a Polymethylene-Interrupted Dienoic Fatty Acid in Seeds of <Emphasis Type="Italic">Arabidopsis thaliana</Emphasis> L.

A cDNA encoding the Arabidopsis extraplastidic linoleate desaturase (FAD3) was overexpressed in the seeds of wild-type Arabidopsis and in a mutant line that accumulates high levels of oleic acid. In the transformed wild-type plants, linolenic acid (18:3Δ9,12,15) increased from 19% to nearly 40% of total seed fatty acids, with a corresponding decrease in linoleate content (18:2Δ9,12). In the high oleate mutant, a large increase in the level of a fatty acid identified by gas-chromatography/mass-spectrometry as mangiferic acid (18:2Δ9,15) was observed. The results demonstrate that the polymethylene-interrupted dienoic fatty acid, mangiferic acid, can be produced in seed oil through the overexpression of a fatty acid n-3 desaturase.

Synthesis,Surface-Active Properties,and Antimicrobial Activities of New Neutral and Cationic Trimeric Surfactants

Neutral and cationic series of new trimeric β-hydroxy amino or ammonium surfactants were synthesized via a two-step process involving the Williamson etherification and regioselective oxirane ring opening with primary and tertiary amines, which afforded good to excellent yields. The synthesized compounds were obtained in high purity by a simple purification procedure on column chromatography. The critical micelle concentration (CMC), effectiveness of surface tension reduction (γ _CMC), surface excess concentration (Γ), and area per molecule at the interface (A) were determined and values indicate that the cationic series is characterized by good surface-active and self-aggregation properties. The antimicrobial activities are reported for the first time against representative bacteria and fungi for trimeric compounds. The antimicrobial potency was found to be dependent on the target microorganism (Gram-positive bacteria > fungi > Gram-negative bacteria), as well as both the neutral or ionic nature (cationic > neutral) and alkyl chain length (tri-C₁₂ > tri-C₁₈ > tri-C₈) of the compounds. The tri-C₈ and tri-C₁₈ compounds were found to be almost inactive and the tri-C₁₂ compounds, the most potent antimicrobial surface-active agents from the synthesized series. The trimeric C₁₂ cationic compound was found to be comparable to benzalkonium chloride against Gram-positive bacteria and fungi, in vitro. The antimicrobial effectiveness of this new compound and the facile two-step procedure for synthesizing it with an excellent overall yield (92%) provide a cost effective trimeric gemini surfactant.

Solubilization,Surface Active and Thermodynamic Parameters of Gemini Amphiphiles Bearing Nonionic Hydrophilic Spacers

A series of novel nine symmetric diquaternary gemini amphiphiles was synthesized having the formula:

Self-Metathesis of 1-Octene Using Alumina-Supported Re<Subscript>2</Subscript>O<Subscript>7</Subscript> in Supercritical CO<Subscript>2</Subscript>

In this contribution we describe the use of heterogeneous catalysts for the liquid-phase self-metathesis of 1-octene in supercritical CO₂. Our work aims at addressing the mass-transfer problems associated with such reaction systems. By coupling a heterogeneous supported Re₂O₇ catalyst with the use of scCO₂, the self-metathesis of 1-octene takes place by and large much more rapidly than in traditional solvent media, and furthermore, by using scCO₂ the overall efficiency and sustainability of the transformation can be improved.

Pure N-Alkylaminopropionic Acid and N-Alkylaminodipropionic Acid Sodium Salts: Synthesis, Characterization, and Physicochemical Properties

Fourteen pure β-aminopropionic acid amphoteric surfactants were synthesized from methyl acrylate using primary amines. The synthesis was done in two steps. First, Michael addition of a primary amine to methyl acrylate gave two separable addition products. Second, because the resulting esters gave, by the classical saponification procedure, undesired retro-Michael products, they were treated with sodium trimethylsilanolate to give the corresponding pure anhydrous acid salt under mild non-aqueous reaction conditions. Two types of amphoteric surfactants were obtained: the monocarboxylate and the dicarboxylate series. The pure surfactants were characterized by IR, ¹H NMR, and ¹³C NMR spectroscopy. The surfactant critical micelle concentrations were evaluated. From these the Gibbs free energy of micellizations [∆G(–CH₂–)_mic] were calculated. These are related to the methylene units that contribute an average of −1.0 (±0.3) kJ mol⁻¹ for both the monocarboxylate and the dicarboxylate series.

<Emphasis Type="Italic">Desmoscaris tripsinosa</Emphasis> and <Emphasis Type="Italic">Palaemonetes africanus</Emphasis> Responses to Concentrations of Neatex and Norust CR486 in Sediment

The assessment of water and sediment quality from chemical pollutants in the Nigerian Niger Delta were conducted using bioindicators (Desmoscaris tripsinosa and Palaemonetes africanus). The Organization for Economic Cooperation and Development (OECD) (2004), No.218 direct sediment toxicity assessment was employed. Shrimp were exposed to sediments treated with Neatex (liquid detergent) and Norust CR 486 (corrosion inhibitor) at concentrations of 31.25, 62.5, 125, 250 and 500 mg/kg. Percentage mortality was measured as the ecological endpoint. Mean % mortality and estimated lethal concentration LC50 values varied with species type, concentration and exposure duration. Observed % mean mortality of the test organisms in both chemicals were significantly different from that of the control test suggesting that mortality may be induced by the effect of the chemicals. LC50s were significantly different for both chemicals at p < 0.05, t = 6.06 (fresh water) and p < 0.05, t = 12.34 (brackish). The values from this study are an indication that the chemicals have the potential to cause acute lethal toxicity. It is a prediction of likely adverse effects on shrimp populations in benthic sediment of the Niger Delta ecological zone. Consequently, there is a great need to protect some of the more sensitive invertebrates representing the major proportion of the diet of many other species.

Synthesis and Biological Activity of 8-Hydroxyquinoline and 2-Hydroxypyridine Quaternary Ammonium Salts

Two series of quaternary cationic surfactant were synthesized by reaction of 8-hydroxyquinoline and 2-hydroxypyridine with long chain alkyl halides (dodecyl, tetradecyl- and hexadecyl-bromide). Surface tension was measured in aqueous solution for different concentrations at 25 °C. Various surface properties of the synthesized surfactants were evaluated, particularly critical micelle concentration (CMC), efficiency (Π_CMC) as well as maximum surface excess (Γ_max) and minimum surface area (A _min). Micellization and adsorption in liquid/air interfaces thermodynamics were investigated. The synthesized cationic surfactants were evaluated for their biocidal activity. All compounds prepared showed good antibacterial and antifungal activities.

Synthesis and Properties of Novel Antifungal Gemini Compounds Derived from <Emphasis Type="Italic">N</Emphasis>-Acetyl Diethanolamines

A series of new N-acetylated non-ionic and cationic gemini surfactants (3a–f) having dimeric structures derived from primary and tertiary amines with variably long tails (C₈–C₁₂–C₁₈) were synthesized. In addition, N-acetylated monomeric analogues 6a and 6b were prepared and their antifungal potency and surface properties were also determined. Critical micelle concentration (CMC), effectiveness of surface tension reduction (γ_CMC), surface excess concentration (Γ), and area per molecule at the interface (A) were also determined and the resulting values indicate that the cationic series is characterized by good surface-active and self-aggregation properties. For the first time, all surfactants were tested to evaluate their antifungal properties using the method for the broth macrodilution test (M27-A2, NCCLS). Four microbial strains were used to perform the study: Candida parapsilosis (ATCC 22019), C. albicans (ATCC 64548), and a wild-type strain of C. parasilosis and Saccharomyces cerevisiae (ATCC 9763). The antimicrobial activity was measured by yeast growth inhibition expressed as minimum inhibitory concentration (MIC) values. Results were compared to those obtained for their monomeric analogues and for a commercially available reference compound (Fluconazole). Gemini 3b, 3e and 3f were found to be the most potent compounds. The results show S. cerevisiae as the most sensitive strain. In contrast, the wild strain of C. parapsilosis was resistant.

Degradation of Pesticides Wastewater by Silyl Based Cationic Surfactants

New stable silayl cationic surfactants have been studied for the destruction of toxic organophosphorus pesticides. Hexadecyl, dodecyl trimethyl silane ammonium chloride or iodide surfactants were synthesized and evaluated in the degradation of pesticides such as Diazinon, Malathion or Chlorpyrifos. The hydrolytic efficiency of each surfactant was tested by measuring the kinetics of model substrates cleavage under a pseudo-first order reaction. The iodo silayl based surfactants showed more destructive power than the chloro derivatives. Meanwhile, the hexadecyl moiety showed more effective pesticide degradation than the corresponding dodecyl moiety.

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