Pyrazole Derived Cationic Surfactants and their Tin and Copper Complexes: Synthesis,Surface Activity,Antibacterial and Antifungal Efficacy

Five membered heterocyclic cationic 3-pyrazolium surfactants namely: 2-[2-(alkyloxy)-2-oxoethyl]-3-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-3-pyrazolium bromide (decyl-; dodecyl-) and their copper and tin complexes were synthesized, their structures were confirmed using different spectroscopic tools. The IR spectra of the metal complexes showed that these compounds exhibit a tetrahedron structure with the transition metal ion (M²⁺) at the center and the cationic ligands arranged in the apexes, while the halide ions in the center. The synthesized compounds were evaluated as biocides against different types of bacteria and fungi. The biological activity data showed that the cationic surfactants exhibit moderate to high efficacy against the tested microorganisms (either bacteria or fungi). While, complexation of these cationic surfactants with Cu (II) and Sn (II) ions the antimicrobial activity was strongly increased. The surface activity of these compounds were discussed and correlated to their chemical structure and the type of substituents on the heterocyclic moiety. Meanwhile, the antimicrobial assay was correlated to the surface activities of the synthesized compounds.     

New Schiff Base Cationic Surfactants: Surface and Thermodynamic Properties and Applicability in Bacterial Growth and Metal Corrosion Prevention

A new series of cationic Schiff bases was synthesized and their chemical structures were confirmed using elemental analysis, infrared spectra and nuclear magnetic resonance. The surface properties of the surfactant solutions including surface tension, effectiveness, efficiency, critical micelle concentration, maximum surface excess and minimum surface area were calculated using surface tension-log concentration profiles. The surface parameters were strongly dependent on the hydrophobic chain length. The thermodynamic properties of the surfactants in their solutions showed the spontaneous behavior of both adsorption and micellization processes. The thermodynamic data revealed that the adsorption of the surfactant molecules at the air/water interface was more favorable than the micellization in the bulk of their solutions. The synthesized surfactants were evaluated with regard to their preventing the corrosion reaction of carbon steel in acidic media and also their acting as antibacterial biocides to inhibit bacterial growth. The data of corrosion and antibacterial evaluations showed the high efficiency and applicability of these compounds in these uses.     

Synthesis,Characterization, Surface and Biological Activity of Diquaternary Cationic Surfactants Containing Ester Linkage

Two series of diquaternary cationic surfactants designated as E9Nm and E11Nm having two different alkyl chains in their chemical structure were synthesized. The chemical structures of these surfactants were confirmed using elemental analysis, FTIR and ¹H‐NMR spectra. The surface activities of the different surfactants were determined using surface and interfacial tension at 25 °C. The surface parameters including: critical micelle concentration, effectiveness, efficiency, maximum surface excess and minimum surface area were determined. The surface activities of the cationic surfactants were correlated with their chemical structure. The surface activities of the surfactants increased with increasing the hydrophobic chain length. The adsorption and micellization tendencies of the surfactants in solution were determined using the free energies of adsorption and micellization. The synthesized surfactants were evaluated as biocides against bacteria and fungi. Biocidal activity data showed that a gradual increase in the hydrophobic chain length of the surfactant molecules gradually increases the efficiency of these surfactants as biocides.     

Surface-Active Properties and Antimicrobial Study of Conventional Cationic and Synthesized Symmetrical Gemini Surfactants

Symmetrical gemini surfactants of cationic series α,ω-alkanediyl bis (dimethyl ammonium bromide) commonly referred as “m–s–m” have been synthesized. Spectral analysis was performed to confirm compound structures and purity. Conductivity and surface tension measurements provide better understanding of the micellization process. Their self-assembly behavior in aqueous solution is also discussed in detail. The antimicrobial efficacy was measured by bacterial and fungal growth inhibition expressed as minimal inhibitory concentration values against five strains of a representative group of microorganisms viz. Bacillus subtilis, Staphylococcus aureus, Klebsiella pneumonia, Salmonella paratyphi B and Aspergillus niger. All of the synthesized surfactants showed antimicrobial activity against them, but at different levels depending on their structures. The surfactants possessing longer alkyl chains (more hydrophobic environment) demonstrated better antimicrobial functionality. The antimicrobial potency was found to be dependent on the representative target microorganism (Gram-positive bacteria > fungi > Gram-negative bacteria), as well as on the ionic nature of the surfactant (cationic), alkyl chain length (m = 12, 16) and spacer length (s = 2, 4, 6) of the synthesized compounds. Gemini surfactants such as 12-2-12 and 12-4-12 were found to be weakly active whereas 16-2-16 and 16-4-16 compounds proved to be the most potent antimicrobial surface-active agents among the synthesized gemini homologues.     

The Effect of Non Ionic Surfactants Containing Triazole, Thiadiazole and Oxadiazole as Inhibitors of the Corrosion of Carbon Steel in 1M Hydrochloric Acid

In the present investigation novel nonionic surfactants were synthesized, characterized and tested as inhibitors of the corrosion of carbon steel in 1M HCl solution. The inhibition action of these surfactants was studied by weight loss, galvanostatic polarization and electrochemical impedance spectroscopy. The adsorption of the inhibitors was well described by the Langmuir adsorption isotherm and the adsorption isotherm parameters were determined at different temperatures. The inhibition efficiency was found to rise when increasing the concentration of these compounds and decreasing the temperature. The effect of temperature on the inhibition efficiency of the corrosion process was studied and the values of some activated thermodynamic parameters were calculated to elaborate the mechanism of inhibition. The synthesized nonionic surfactants exhibit good surface and antimicrobial properties.     

Corrosion Inhibition by Some Cationic Surfactants in Oil Fields

Two cationic surfactants, namely, tetradecyl dimethyl benzyl ammonium chloride (TDBAC) and tributyl tetradecyl phosphonium chloride (TTPC) were supplied from the local market and characterized. The adsorption tendency of the two surfactants was estimated from the values of the depression of surface tension of the water at the critical micelle concentration. The studied surfactants were evaluated as antimicrobial agents against sulfate-reducing bacteria. These cationic surfactants showed good antimicrobial activities against the tested microorganisms. It was also found that these compounds are good corrosion inhibitors for carbon steel in 0.5?M HCl at doses of 25?C600?ppm.     

双子季铵盐循环水管道减阻剂合成和性能评价

为解决现有季铵盐表面活性剂减阻剂腐蚀普通碳钢循环水管道问题,首次研究将双子季铵盐表面活性剂作为循环水管道减阻剂应用。用椰油基二羟乙基胺与二溴乙烷、环氧氯丙烷和二氯乙醚反应合成了3种双子季铵盐表面活性剂,并在试验装置上对减阻剂配方的减阻性能和缓蚀性能进行了评价。在减阻剂质量浓度1 000 mg/L,循环水流速3 m/s和循环水温度10~70℃的优化实验条件下,减阻剂对碳钢循环水管道减阻率可达69.1%,缓蚀率可达95.0%。     

Characterization,surface properties and biological activity of some synthesized anionic surfactants

In this study, esterification reaction between four different fatty alcohols (octyl, dodecyl, hexdecyl and octadecyl alcohol) and phosphoric acid was performed. The produced compound was reacted with polyethylene glycol-400. Then, the reaction product was quenched using sodium hydroxide to form the desired anionic gemini surfactants. The chemical structures of the synthesized surfactants were recognized by FT-IR and ¹H NMR spectroscopy. The synthesized surfactants showed higher surface activity. The emulsion stability measurements showed the applicability of these surfactants as emulsifying agents. The foaming power measurements showed the synthesized surfactants have low ability to foam formation. The thermodynamic parameters showed their tendency toward adsorption at the interfaces and also micellization in the bulk of their solutions. The studied surfactants were evaluated as antimicrobial agents against pathogenic bacteria using inhibition zone diameters. The synthesized surfactants showed good antimicrobial activities against the tested microorganisms including Gram positive, Gram negative as well as fungi. The promising inhibition efficiency of these compounds against the pathogenic bacteria facilitates them to be applicable in the petroleum field as new categories of biocides.     

Synthesis of Bis[<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>′-(alkylamideethyl)ethyl] Triethylenediamine Bromide Surfactants and Their Oilfield Application Investigation

Bis[N,N′-(alkylamideethyl)ethyl] triethylenediamine surfactants are quaternary ammonium salt Gemini surfactants with amide, which are synthesized from fatty acid (dodecanoic, hexadecanoic, tetradecanoic and octadecanoic) methyl esters, triethylene tetramine and ethyl bromide. The chemical structures of the prepared compounds were characterized by elemental analysis, FTIR and ¹H-NMR spectra, melting point and Krafft point. Several properties of the synthesized surfactants were studied including surface tension, critical micelle concentration, interfacial tension, emulsification power, salt effect, corrosion inhibition efficiency and biological activity. The results show that the surface activity, critical micelle concentration and interfacial activity are correlated to their chemical structures. The emulsification power measurements of these surfactants show their low emulsifying tendency towards Tazhong’s crude oil from Tarim Oilfield. The synthesized surfactants also exhibit high biocidal activity towards Gram-positive and Gram-negative bacteria and fungi. This activity increases with the increase of alkyl chain length. The corrosion measurement of these surfactants in acidic media with a weight loss technique show good protection of mild steel alloys against acidic environments. These properties suggest that the synthesized compounds have potential for application in the oilfield area.     

Effects of structure of the ionic head of cationic surfactant on its inhibition of acid corrosion of mild steel

Two n-alkyl-quaternary ammonium compounds were studied as corrosion inhibitors for acid corrosion of mild steel using electrochemical and weight loss methods. The two compounds are hexadecylpyridinium bromide (HDPB) and hexadecyltrimethyl ammonium bromide (HDTB). The influence of the structure of the ionic head on the inhibition action of the two cationic surfactants was studied by analyzing the data at different concentrations and temperatures. The inhibition efficiency increases with the concentration. It increases with temperature in the case of HDPB but decreases in the case of HDTB. The apparent activation energy, E _a of corrosion in the presence of HDPB was found to be lower than in blank (0.5 m H₂SO₄). In the case of HDTB, E _a was larger than that of the blank. A larger extent of adsorption for HDPB on the metal surface was evident from the larger negative values of the free energy of adsorption. The results yielded the extent and mode of adsorption of the inhibitors on mild steel. The stronger adsorption of HDPB was attributed to the differences in the molecular structures of the inhibitors.     

CORROSION INHIBITION OF STEEL PIPELINES IN OIL WELL FORMATION WATER BY A NEW FAMILY OF NONIONIC SURFACTANTS

A new family of nonionic surfactants was synthesized and evaluated as corrosion inhibitors for steel pipelines in oil well formation water. Polarization data show that the selected surfactants act as mixed-type inhibitors. EIS results show that the change in impedance parameters (R_t and C_dl) with the concentration of the surfactants studied is indicative of the adsorption of surfactant molecules on carbon steel surface, leading to formation of a good protective film. The properties of this film were studied by various surface analysis tools. Finally, the relation between the surface properties of the inhibitor molecules and corrosion inhibition efficiency is discussed.     

Screening for Potential Antimicrobial Activities of Some Cationic Uracil Biocides Against Wide-Spreading Bacterial Strains

Eight novel uracil-based cationic surfactants containing Schiff base species were synthesized and characterized using elemental analysis, FTIR, ¹H-NMR and ¹³C-NMR spectroscopy. The surface activities of the synthesized Schiff bases and their cationic derivatives were determined based on interfacial tension measurements and partition coefficient values in water/octanol system. The synthesized Schiff bases and their cationic derivatives were evaluated as novel biocides against different bacteria and fungi strains. The results showed that the biocidal activity of the synthesized Schiff bases was considerably increased by quaternization. The influence of the cationic surfactants as biocides was increased by increasing the hydrophobic chain length and the presence of the methoxy groups. The biocidal activity was also increased by increasing the partition coefficient in water/octanol system. The structure and surface activity/biocidal activity of the different compounds were discussed.     

Synthesis of Quaternary,Long-Chain N-Alkyl Amides and Their Corrosion Inhibition in Acidic Media

New cationic surfactants were synthesized by the quaternization of a number of straight-chain amide derivatives with triethylamine or pyridine. The corrosion inhibition tests of the surface-active compounds were performed at room temperature for 24 h on carbon steel coupons in acidic media using the gravimetric method. The acidic media used were 1.5 M HCl and 1.5 M H₂SO₄. Almost all of the synthesized cationic surfactants showed efficient inhibition of corrosion in the test. To establish the inhibition efficiencies of the inhibitors, surface characterization studies (contact angle measurements, SEM analysis and optical profilometer images) of the metal coupons used were performed.     

Bitumen–solids attachment induced by cation activation

Interactions between negatively charged bitumen and fine solids under oil sands extraction conditions were simulated using mature fine tailings (MFT) and hydrocarbon oil with dissolved carboxylic acids. Their attachment induced by cation activation was evaluated with different types of cations by simple dynamic attachment tests. The results revealed that solid hydrophobization by adsorbing surfactants was key for oil–solid attachment. Activation by multivalent metal cations was due to surface precipitation of metal hydroxides, followed by chemisorbing anionic surfactants on metal-activated solids to form metal carboxylate complexes/precipitates, thereby hydrophobizing the solids. Activation by cationic surfactants depended on their hydrocarbon chain lengths. For short hydrocarbon chains, where hydrophobic interaction is weaker than electrostatic interaction between the added cationic and anionic surfactants, the added cations promote the adsorption of anionic surfactants by electrostatic interaction to render the solids hydrophobic. For long hydrocarbon chains where hydrophobic interaction is stronger than electrostatic interaction between the added cationic and anionic surfactants, the adsorption of anionic surfactants occurs through the hydrophobic association of the hydrocarbon chains, posing the head group towards water, thereby making the solids less hydrophobic. Activation by cationic flocculants was purely physical (hydrogen bonding and electrostatic): when the solids were turned positive by the added cationic flocculants, the added anionic surfactants then adsorbed onto the solids to render them hydrophobic. It appeared that soluble multivalent metal species (e.g., Ca²⁺ and Mg²⁺) were much less harmful to bitumen extraction than those heavy metals coated on the solids, either in the form of surface precipitates or hydrolyzed ionic species.     

Synthesis and Evaluation of 4-Diethyl Amino Benzaldehyde Schiff Base Cationic Amphiphiles as Corrosion Inhibitors for Carbon Steel in Different Acidic Media

A novel series of cationic surfactants containing Schiff base groups were synthesized by condensation of fatty amines namely: dodecyl, tetradecyl, hexadecyl and octadecyl amine and 4-diethyl aminobenzaldehyde. The chemical structures of these surfactants were confirmed using elemental analysis, FTIR spectra, ¹H-NMR and atomic absorption spectroscopy. Surface properties of the synthesized compounds were determined using surface tension techniques. The results of the surface tension measurements showed good surface behaviors of these compounds in their aqueous solutions. The surface activities were found to be greatly influenced by the chemical structures of the synthesized compounds. The synthesized cationic Schiff bases were evaluated as corrosion inhibitors for carbon steel in different acidic media (HCl and H₂SO₄) at different doses (400, 200, 100, 50, 25 ppm). The corrosion inhibition efficiencies of these inhibitors were calculated using the corrosion rates of the carbon steel in the studied media and found in the acceptable range of the commercially used inhibitors. Also the chemical structure of these inhibitors was found of great influence on their inhibiting efficiency.     

The Effects of Amide Bonds and Aromatic Rings on the Surface Properties and Antimicrobial Activity of Cationic Surfactants

The cationic surfactants containing aromatic rings and amide bonds, N,N-dimethyl-N-dodecyl-2-pyrimidinylcarbamoylmethyl ammonium chloride ( a ), N,N-dimethyl-N-dodecyl-2-thiazolylcarbamoylmethyl ammonium chloride ( b ), and N,N-dimethyl-N-dodecyl-phenylcarbamoylmethyl ammonium chloride ( c ), were synthesized and characterized. The surface tension and conductivity values were employed to investigate the absorption and micellization behavior of the three cationic surfactants. The results showed that the synthesized surfactants have shown a low critical micelle concentration (CMC) and a high adsorption efficiency (pC₂₀) compared with the traditional cationic surfactant of N,N-dimethyl-N-dodecyl-N-benzyl ammonium chloride ( BAC-12 ). The aromatic rings of the a , b , and c molecular structures were analyzed using the ¹H NMR spectra for electrostatic repulsion effects between hydrophilic headgroups. The size distribution of the micelles was derived using dynamic light scattering (DLS) techniques. In addition, the foaming ability of a , b , c , and BAC-12 was investigated and the antimicrobial activity of a , b , c , and BAC-12 against Escherichia coli, Staphylococcus aureus, and Bacillus subtilis was examined. The effects of amide bonds and aromatic rings on the surface properties and antimicrobial activity of a , b , and c were analyzed and compared with BAC-12 of the same alkyl chain length. The synthesized surfactants exhibited a high surface ability and better antibacterial activity compared with BAC-12 .     

Imidazolium,Pyridinium and Dimethyl-Ethylbenzyl Ammonium Derived Compounds as Mixed Corrosion Inhibitors in Acidic Medium

Seven cationic surfactants: 1-methyl-3-tetradecyl imidazolium bromide, 1-methyl-3-hexadecyl imidazolium bromide, N,N-tetradecyl pyridinium bromide, N,N-hexadecyl pyridinium bromide, N,N-dimethyl-N-ethylbenzyl ammonium bromide, N,N-dimethyl-N-ethylbenzyl ammonium laurate and N,N-dimethyl-N-ethylbenzyl ammonium acetate, were investigated at different doses (10, 25, 50, 100, and 200 ppm) as corrosion inhibitors for steel grade API 5L X52 in hydrochloric acid 2 M using a weight loss technique, impedance and polarization resistance methods. The corrosion inhibition of steel grade API 5L X52 of the cationic surfactants was attributed to their molecular structure (heterocyclic ring, hydrophobic chain length and counterion) that enhances adsorption onto steel surface. The best protective efficiency of the film was higher than 90% (N,N-Dimethyl-N-ethylbenzyl ammonium acetate). It is important to know how organic inhibitor films grown on the metallic surface in order to achieve superior corrosion inhibition, hence experimental findings were described by Langmuir adsorption isotherm. The Electrochemical Impedance Spectroscopy spectrums were fitted by means of the Voigt model.     

Synthesis and Characterization of Cationic Surfactants Based on N‐Hexamethylenetetramine as Active Microfouling Agents

Four cationic surfactants of quaternary hexammonium silane chloride based on hexamethylenetetramine and alkyl chloride were synthesized. The chemical structures of the prepared cationic surfactants were elucidated using Fourier transform infrared (FT‐IR) spectroscopy and mass spectrometry analysis. The surface and thermodynamic properties of the prepared surfactants were also studied. The performance of these cationic surfactants as microfouling agents against two strains of Gram‐negative bacteria, namely, Pseudomonas aeruginosa and Escherichia coli, and two strains of Gram‐positive bacteria, namely, Staphylococcus aureus and Bacillus subtilis, were evaluated as antimicrobial agents. The results showed that the maximum antimicrobial activity was detected for N‐hexamethylenetetramine‐N‐ethyl silane ammonium trichloride (Ah). The maximum and minimum antimicrobial activities were 73 and 60 % against S. aureus and E. coli, respectively, at a concentration of 5 mg/l, pH 7, and 37 °C.     

New Biodegradable Nonionic-Anionic Surfactants Based on Different Fatty Alcohols as Corrosion Inhibitors for Aluminum in Acidic Medium

Two series of eco-friendly nonionic anionic surfactants based on itaconic acid and 1, 6 hexane diol were synthesized. The chemical structures of the prepared surfactant were confirmed by FTIR and ¹H NMR spectroscopy. The prepared surfactants were evaluated to prevent the corrosion of aluminum in 1.0 M HCl solution by electrochemical and chemical methods. The data obtained showed that the prepared compounds have good inhibition efficiency (IE%) even at 10⁻⁵ M concentrations and act as mixed-type inhibitors, they do not affect the mechanism of the electrode processes, as well as the IE% increase by increasing the concentrations of the inhibitors, immersion time, and hydrophilic chain length. The high inhibition efficiency is due to the adsorption of the inhibitors molecules on the metal surface and the formation of a protective film. The surface activities of these compounds were also investigated and were correlated to their inhibition efficiencies and chemical structure. Through studying biodegradability of the synthesized surfactants we find that they are readily biodegradable in the environment and thus they are considered as eco-friendly corrosion inhibitors. Finally, the effect of the addition of these compounds on the aluminum surface was identified by atomic force microscopy (AFM) technique.     

Interactions between Anionic Polyacrylamide and Cationic Gemini/Conventional Surfactants

The interaction of anionic polymer polyacrylamide and cationic Gemini surfactants, namely: α,ω-bis(hexadecyldimethylammonium)alkane dibromides, (16-s-16), s = 5, 6 and their conventional counterpart cetyltrimethylammonium bromide (CTAB) has been investigated by electrical conductivity, rheology, and scanning electron microscopy (SEM) techniques. Stronger interaction of Gemini surfactants in comparison to their conventional counterpart CTAB was observed from conductivity studies, while viscosity studies show that the interaction is quite significant with Gemini surfactants. The thermodynamic parameters for interactions show feasibility of interaction between the polymer and surfactant. SEM results support the viscosity data.