Synthesis,Surface Property and Antimicrobial Activity of Cationic Gemini Surfactants Containing Adamantane and Amide Groups

A series of novel cationic gemini surfactants, namely 1,3-adamantanedicarboxylic acid bis(alkyldimethyl-3-ammoniopropyl amide) dibromide designated as [Ad-2(amC _n )] (n = 12, 14, 16), containing adamantane, two amide groups, and two hydrocarbon chains, were synthesized from 1,3-adamantanedicarboxylic acid. The surface-active properties of the surfactants were investigated through surface tension and electrical conductivity measurement. A series of thermodynamic parameters such as standard free energy \(\left( {\Delta G^\circ_{\text{m}} } \right)\) , enthalpy \(\left( {\Delta H^\circ_{\text{m}} } \right)\) , and entropy \(\left( {\Delta S^\circ_{\text{m}} } \right)\) of micellization were evaluated from electrical conductivity measurements in the temperature range from 288 to 308 K. The micellization for [Ad-2(amC _n )] is entropy-driven at low temperature and enthalpy-driven at high temperature. Further, the antimicrobial activity of the synthesized gemini surfactants against both Gram-positive and Gram-negative bacteria was also investigated, and this study showed that the compound [Ad-2(amC₁₂)] has excellent antibacterial activity against all studied bacteria.     

Synthesis,Surface and Antimicrobial Activities of Novel Cationic Gemini Surfactants

A series of novel cationic gemini surfactants [C_nH_2n+1–O–CH₂–CH(OH)–CH₂–N⁺(CH₃)₂–(CH₂)₂]₂·2Br^? [ 3a (n = 12), 3b (n = 14) and 3c (n = 16)] having a 2‐hydroxy‐1,3‐oxypropylene group [?CH₂–CH(OH)–CH₂–O–] in the hydrophobic chain have been synthesized and characterized. Their water solubility, surface activity, foaming properties, and antibacterial activity have been examined. The critical micelle concentration (CMC) values of the novel cationic gemini surfactants are one to two orders of magnitude smaller than those of the corresponding monomeric surfactants. Furthermore, the novel cationic gemini surfactants have better water solubility and surface activity than the comparable [C_nH_2n+1–N⁺(CH₃)₂–(CH₂)₂]₂·2Br^? (n‐4‐n) geminis. The novel cationic gemini surfactants 3a and 3b also exhibit good foaming properties and show good antibacterial and antifungal activities.     

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.     

Novel Imidazolium-Based Gemini Surfactants: Synthesis, Surface Properties, Corrosion Inhibition and Biocidal Activity Against Sulfate-Reducing Bacteria

Three novel imidazolium-based gemini surfactants had been synthesized and characterized using different spectroscopic techniques. The surface properties of the synthesized surfactants were determined using surface tension measurements at 20 °C. The surface parameters including critical micelle concentration (CMC), π _CMC, Pc₂₀, Γ_max and A _min were determined. The synthesized compounds were evaluated as corrosion inhibitors for carbon steel in 0.5 M HCl solution using the weight loss and polarization techniques. The biological activity of these surfactants was evaluated against sulfate reducing bacteria using most probable number method. The results indicate that the synthesized compounds have good surface properties and are proper corrosion inhibitors for low carbon steel, with a high inhibition efficiency observed around their CMC. These compounds exhibit a significant biocidal activity against sulfate reducing bacteria.     

Synthesis,Surface and Antimicrobial Activities of Cationic Gemini Surfactants with Semi-Rigid Spacers

Four cationic gemini surfactants featuring semi-rigid spacers were synthesized via a two-step process. The surface-active properties of these surfactants were investigated through surface tension and electrical conductivity measurement. The thermodynamic parameters of micellization were evaluated from electrical conductivity measurements at temperatures ranging from 293 to 313 K. The aggregation behavior of these synthesized gemini surfactants in water were investigated using dynamic light scattering and transmission electron microscopy. Further, the antimicrobial activities of these synthesized gemini surfactants against both Gram-positive and Gram-negative bacteria were also investigated.     

Synthesis and Properties of Novel Phenylenediamine Gemini Surfactants

In the present work, a two-step method was adopted to synthesize a series of novel Gemini surfactants using N,N-dimethylalkyl amines (alkyl length = C₁₂, C₁₆ and C₁₈), epichlorohydrin, and n-phenyllenediamine as starting materials. The products were characterized using mass spectroscopy (MS) and nuclear magnetic resonance spectroscopy (¹H NMR). Systematic experiments were conducted to evaluate their surface activity, foaming properties, and antibacterial performance. Results showed the critical micelle concentrations (CMC) of the C₁₂-based, C₁₆-based, and C₁₈-based phenylenediamine surfactants were 3.295 × 10⁻³, 2.532 × 10⁻⁴, and 3.140 × 10⁻⁴ mol L⁻¹ at 298 K, respectively, with corresponding surface tension (γ_cmc) values of 28.24, 31.95, and 35.06 mN m⁻¹ under the same conditions. The Gemini surfactants showed not only good surface activity and foaming properties, but also demonstrated good antimicrobial performance against Gram-positive and Gram-negative bacteria and fungi.     

Synthesis and Evaluation of Novel Amido-Amine Cationic Gemini Surfactants Containing Flexible and Rigid Spacers

New amido‐amine‐based cationic gemini surfactants with flexible and rigid spacers and different hydrophobic tails were synthesized and characterized. These gemini surfactants were prepared by a modified procedure through amidation of long chain carboxylic acids using 3‐(dimethylamino)‐1‐propylamine followed by treatment with halohydrocarbons. The effect of the trans and cis conformation of the spacer double bond was investigated by means of critical micelle concentration, surface tension reduction, and thermal stability. The short‐term thermal stability of the gemini surfactants was assessed using thermogravimetric analysis (TGA) and the long‐term thermal stability was examined by a unique approach based on structure characterization techniques including NMR (¹H and ¹³C) and FTIR analysis. TGA results demonstrated excellent short‐term thermal stability since no structure degradation was observed up to 200 °C. Structural characterization revealed impressive long‐term thermal stability of the gemini surfactants with no structure decomposition after exposing them to 90 °C for 10 days. The critical micelle concentration of gemini surfactants was found to be in the range of 0.77 × 10^?4–3.61 × 10^?4 mol L^?1 and corresponding surface tension (γ_CMC) ranged from 30.34 to 38.12 mN m^?1. The surfactant with the trans conformation of spacer double bond showed better surface properties compared to the surfactant with the cis conformation of spacer double bond. Similarly, increasing surfactant tail length and spacer length resulted in decreasing CMC values. Moreover, bromide counterion showed improved surface properties compared to chloride counterion.     

Preparation,Characterization and Properties of Novel Cationic Gemini Surfactants with Rigid Amido Spacer Groups

A series of novel cationic gemini surfactants with rigid amido groups inserted as the spacers, named C ₁₂ ‐PPDA‐C ₁₂ , C ₁₄ ‐PPDA‐C ₁₄ and C ₁₆ ‐PPDA‐C ₁₆ , were synthesized by a two‐step reaction with dimethyl terephthalate, N,N‐dimethyl propylene diamine and alkyl bromide as raw materials. The chemical structures of the prepared compounds were confirmed by IR, ¹H and ¹³C NMR and element analysis. Surface activity properties of the synthesized compounds were investigated by surface tension, electrical conductivity and fluorescence. Increasing the number of carbon atoms in the hydrophobic alkyl chain, decreased the critical micelle concentration (CMC), surface tension at the CMC and the minimum surface area. Other relevant properties including foaming ability and emulsion stability were investigated. The results indicated that the synthesized gemini surfactants possess good surface properties, emulsifying properties and steady foam properties.     

Gemini Cationic Surfactants: Synthesis and Influence of Chemical Structure on the Surface Activity

Three cationic gemini surfactants were synthesized and characterized using different methods. Their surface activities were measured using surface and interfacial tension measurements. The effect of the spacer chain length on the surface activity, emulsification power and interfacial tension was studied. The thermodynamic parameters showed the tendency towards micellization and adsorption. The results showed that longer spacers increased the micellization tendencies of the surfactants, while shorter spacers increased the adsorption tendency at the air–water interface.     

Synthesis,Surface Activity and Aggregation Behavior of Novel Gemini Pyridinium Amphiphiles

A series of novel pyridinium cationic gemini amphiphiles, 3,3′-(carbonyldiimino)bis (1-n-alkylpyridinium) dibromides, having octyl, decyl, dodecyl, tetradecyl alkyl chains were synthesized. The surface properties and aggregation behavior in aqueous solution were evaluated by surface tension, dynamic light scattering (DLS), and transmission electron microscopy (TEM) measurement. The adsorption at the air/solution interface of all the compounds were quantitative described using the Frumkin model, and the effect of alkyl chain length on surface activity and aggregate behavior was analyzed. It was found that all the gemini amphiphiles possess surface activity and low critical micellization concentration (CMC) values. The values of log CMC depended linearly on the carbon number of the alkyl chains, but the surface tension at the CMC (γ_cmc) showed a minimum for the compound with dodecyl chains. Combinations of DLS and TEM observations showed the existence of vesicles with a broad size distribution in aqueous solution. Meanwhile, vesicles formed below the CMC could be a possible reason for the observed deviation of surface tension curves from the Frumkin model.     

A Comprehensive Study on the Synthesis and Micellization of Disymmetric Gemini Imidazolium Surfactants

Two groups of disymmetric Gemini imidazolium surfactants, [C₁₄C₄C _m im]Br₂ (m = 10, 12, 14) and [C _m C₄C _n im]Br₂ (m + n = 24, m = 12, 14, 16, 18) surfactants, were synthesized and their structures were confirmed by ¹H NMR and ESI–MS spectroscopy. Their adsorption at the air/water interface, thermodynamic parameters and aggregation behavior were explored by means of surface tension, electrical conductivity and steady-state fluorescence. A series of surface activity parameters, including cmc, γ _cmc, π _cmc, pC ₂₀, cmc/C ₂₀, Γ _max and A _min, were obtained from surface tension measurements. The results revealed that the overall hydrophobic chain length (N _c) for [C₁₄C₄C _m im]Br₂ and the disymmetry (m/n) for [C _m C₄C _n im]Br₂ had a significant effect on the surface activity. The cmc values decreased with an increase of N _c or m/n. The thermodynamic parameters of micellization (ΔG _m ^θ , ΔH _m ^θ , ΔS _m ^θ ) derived from the electrical conductivity indicated that the micellization process of [C₁₄C₄C _m im]Br₂ and [C _m C₄C _n im]Br₂ was entropy-driven at different temperatures, but the contribution of ΔH _m ^θ to ΔG _m ^θ was enhanced by increasing N _c or m/n. The micropolarity and micellar aggregation number (N _agg) were estimated by steady-state fluorescence measurements. The results showed that the surfactant with higher N _c or m/n can form larger micelles, due to a tighter micellar structure.     

Preparation of a Novel Class of Cationic Gemini Imidazolium Surfactants Containing Amide Groups as the Spacer: Their Surface Properties and Antimicrobial Activity

A class of novel cationic Gemini imidazolium surfactants containing amide groups as the spacer were synthesized from ethylenediamine and 1-bromoalkane(C₈, C₁₀, C₁₂, C₁₄, C₁₆) by N-alkylation to get N,N′-dialkyl ethylenediamine (1a–e), 1a–e was further reacted with chloroacetyl chloride by N-acylation to get N,N′-(ethane-1,2-diyl)bis(2-chloro-N-alkylacetamide) (2a–e), which was further reacted respectively with 1-methyl imidazole by quaternized to form the surfactant molecule, N,N′-((ethane-1,2-diyl)bis(alkyl-azanediyl)bis(2-oxoethane-2,1-diyl)) bis(1-methyl-1H-imidazol-3-ium) dichloride. The structures of intermediates (1a–e) and (2a–e) were characterized by IR and ¹H NMR. The structures of the surfactants (3a–e) were characterized by IR, ¹H-NMR and ¹³C-NMR and element analysis. The critical micelle concentrations (CMC) of 3a–e were determined by the conductivity method at 25 °C. The CMC values decreased with increasing the length of the hydrophobic chain. The surfactants (3a–e) showed good foaming stability, emulsion ability and wetting ability. The surfactants (3a–e) also have good antimicrobial activity against Staphylococcus aureus, Escherichia coli and Bacillus subtilis.     

Synthesis,Characterization and Evaluation of the Surface Active Properties of Novel Cationic Imidazolium Gemini Surfactants

New imidazolium gemini surfactants were synthesized by reaction of epichlorohydrin with long chain fatty alcohols furnishing products 2-(alkoxymethyl)oxirane followed by their subsequent treatment with imidazole resulting in the formation of 1-(1H-imidazol-1-yl-3 alkoxy)propane-2-ol which on subsequent treatment with 1,2-dibromoethane and 1,3-dibromopropane resulted in the formation of title gemini surfactants:1,2-bis(1(3-alkoxy-2-hydroxypropyl)-1H-imidazol-3-ium)ethane bromide (7), 1,3-bis(1(3-alkoxy-2-hydroxypropyl)-1H-imidazol-3-ium)propane bromide (8), 1,2-bis(1(3-alkoxy-2-hydroxypropyl)-1H-imidazol-3-ium)ethane bromide (9), 1,3-bis(1(3-alkoxy-2-hydroxypropyl)-1H-imidazol-3-ium)propane bromide (10), 1,2-bis (1(3-alkoxy-2-hydroxypropyl)-1H-imidazol-3-ium)ethane bromide (11) and 1,3-bis (1(3-alkoxy-2-hydroxypropyl)-1H-imidazol-3-ium)propane bromide (12). Their identification was based on IR, ¹H-, ¹³C-NMR, DEPT, COSY and mass spectral studies. Their surface active properties were also evaluated on the basis of surface tension and conductivity measurements.     

Physico-Chemical Investigations of Mixed Micelles of Cationic Gemini and Conventional Surfactants: a Conductometric Study

The interaction of cationic gemini and cationic conventional surfactants by conductivity was systematically overviewed, paying attention to synergism observed in micellization. These mixed systems were found to show remarkable synergism in micelle formation. The experimental critical micelle concentration values being lower than the value predicted by ideal solution theory indicate that the mixed micellization is due to attractive interaction between the two components. Gemini/conventional systems form mixed micelle due to attractive interactions (negative β values). The values of micellar mole fraction of constituent 1 (X ₁) in surfactant mixtures are more than in the ideal state (X ₁ ^ideal ), which means that, the mixed micelles are rich in conventional surfactants in comparison to that in the ideal state.     

Gemini Pyridinium Surfactants: Synthesis and Their Surface Active Properties

New pyridinium Gemini surfactants have been synthesized by esterification of renewable fatty acids with halogenated alcohols furnishing respective esters (2‐chloroethyl hexadecanoate, 2‐chloroethyl tetradecanoate, 2‐chloroethyl dodecanoate, 2‐bromoethyl hexadecanoate, 2‐bromoethyl tetradecanoate and 2‐bromoethyl dodecanoate) followed by their subsequent treatment with 4,4′‐trimethylenedipyridine resulting into the formation of title Gemini surfactants: (4,4′‐(propane‐1,3‐diyl)bis(1‐(2‐(hexadecanoyl oxy) ethyl) dipyridinium chloride(7), (4,4′‐(propane‐1,3‐diyl)bis(1‐(2‐(tetradecanoyl oxy) ethyl) dipyridinium chloride (8), 4,4′‐(propane‐1,3‐diyl)bis(1‐(2‐(dodecanoyl oxy) ethyl) dipyridinium chloride (9), (4,4′‐(propane‐1,3‐diyl)bis(1‐(2‐(hexadecanoyl oxy) ethyl) dipyridinium bromide (10), (4,4′‐(propane‐1,3‐diyl)bis(1‐(2‐(tetradecanoyl oxy) ethyl) dipyridinium bromide (11), 4,4′‐(propane‐1,3‐diyl)bis(1‐(2‐(dodecanoyl oxy) ethyl) dipyridinium bromide (12). Their identifications are based on IR, ¹H‐, ¹³C‐NMR, DEPT, COSY and mass spectral studies. Their surface active properties are also evaluated on the basis of surface tension and conductivity measurements and thermal stability of these long chain cationics Gemini surfactants have been measured by thermal gravimetric analysis under nitrogen atmosphere.     

Synthesis,Characterization, Surface,and Thermodynamic Studies of Alkyl Tetrachloroferrates: Performance Evaluation of Their Nanostructures as Biocides

Decyl and dodecylamino tetrachloroferrates were synthesized and characterized using Fourier-transform infrared spectroscopy (FTIR), elemental analysis, X-ray diffraction (XRD), nuclear magnetic resonance (¹H-NMR), and atomic absorption spectroscopy (AAS). The surface properties of the cationic surfactants including critical micelle concentration, effectiveness, minimum surface area, and maximum surface excess were determined using surface tension measurements. The effectiveness of surface tension reduction (π_cmc) was found to increase as the hydrophobic chain length increases with values of 30 and 34 mN m⁻¹ for C₁₀ and C₁₂, respectively. Moreover, the effect of temperature on micellization was determined over the range of 35–55 °C. Thermodynamic parameters (ΔG°, ΔS°, and ΔH°) were calculated and the results indicate a spontaneous process for both micellization and adsorption. The nanoparticles (NC₁₀ and NC₁₂) of the prepared surfactants were obtained using the ball mill technique. The particle size and morphology of the nanoparticles were determined using transmission electron microscope measurements. The antibacterial study of the nanoparticle surfactants revealed their strong efficiency against fungi and different pathogenic bacteria compared with the original surfactants.     

Synthesis, Surface Active Properties of Novel Gemini Surfactants with Amide Groups and Rigid Spacers

A series of novel cationic gemini surfactants, bis-(N-(3-alkylamido-propyl)-N,N-dimethyl)-p-phenylenediammonium dichloride, were synthesized. The structures of the gemini surfactants were characterized by IR, ¹H NMR and ¹³C NMR. The Krafft temperatures of surfactants were determined through conductivity, the surface active properties in aqueous solution were studied at various temperatures by surface tension and conductivity. The thermodynamic functions of micellization process of the surfactants were also calculated by conductivity. The Krafft temperatures of the surfactants were 12, 13 and 28 °C. The values of CMC and Γ _max decreased with increasing the length of hydrophobic chains, but the values of CMC and α increased with increasing temperature. The process of micellization is a spontaneous, exothermic and entropy-driven process.     

Waste Cooking Oil-Based Novel Gemini Imidazolinium Surfactants With Carbonate Linkage: Green Synthesis,Characterization and Properties Evaluation

Imidazolinium surfactants belong to the category of cationic surfactants that have already gained the great interest of researchers due to their varied range of commercial applications. With the advancement in the field of surfactants research, imidazolinium surfactants are being converted into their corresponding gemini surfactants. Gemini surfactants are known to have exceptional self‐assembling characteristics and exclusive interfacial activity that include much lower CMC and better ability to reduce surface tension than their conventional monomeric counterparts. Long reaction time associated with conventional thermal synthetic procedures and high production costs are the two major issues involved in the synthesis of gemini surfactants. The present research work involves the microwave synthesis of novel gemini imidazolinium surfactants with carbonate linkage. In order to synthesize cost effective gemini surfactants, waste cooking oils have been used as raw materials. Structural characterization of synthesized gemini surfactants has been achieved through ¹H‐NMR, ¹³C‐NMR and FT‐IR.     

Novel Phospholium-Type Cationic Surfactants: Synthesis,Aggregation Properties and Antimicrobial Activity

A series of novel phospholium amphiphilic compounds with straight alkyl chains with different numbers of carbon atoms (12, 14, 15, 16, 17, 18) were synthesized. The quaternary phosphorus, phosphonium cation, is incorporated into a five-membered heterocyclic ring. Their physicochemical properties were investigated by measurements of surface tension, conductivity and dynamic light scattering. The critical micelle concentration (c _M), the surface tension value at the c _M (γ _cmc), the surface area at the surface saturation per head group (A _cmc), the ionization degree of micelle (α), the free energy of micellization (ΔG° _mic), and hydrodynamic diameter (d _h) were determined. Antimicrobial activity was tested against bacteria and yeast. The structure–activity relationship was determined.