Surface Properties and Biological Activity of Select Cationic Surfactants

A series of cationic surfactants, N-(decyl N-tri-ethanol ammonium Bromide) (C₁₀), N-(dodecyl N-triethanol ammonium Bromide) (C₁₂), N-(hexadecyl N-triethanol ammonium Bromide) (C₁₆) were synthesized. These compounds have been evaluated by studying their surface properties, surface parameters, biodegradability and antimicrobial and antifungal activities.

Surface and Aggregation Properties of Synthesized Cetyl Alcohol Based Bis-Sulfosuccinate Gemini Surfactants in Aqueous Solution

A series of cetyl alcohol based anionic bis‐sulfosuccinate gemini surfactants (BSGSCA1,4; BSGSCA1,6 and BSGSCA1,8) with different spacer lengths was prepared using dibromoalkanes. The surfactant structure was elucidated using elemental analysis, Fourier transform infrared spectroscopy (FT‐IR) and nuclear magnetic resonance spectroscopy (NMR). Surface tension measurements were used to determine the critical micelle concentration (CMC), the surface tension at the CMC (γ_CMC), surface pressure at the CMC (π_CMC) and efficiency of adsorption (pC20). On the basis of surface studies, the CMC and γ_CMC decreases with increasing length of the spacer group. The micelle aggregation number, determined by fluorescence quenching studies, increases with increasing surfactant concentration above the CMC. The micropolarity in the micelle increases with increasing length of the spacer and decreases with increasing surfactant concentration.     

Synthesis and Surface Properties of Novel Gemini Imidazolium Surfactants

Five new Gemini imidazolium surfactants were synthesized from imidazole and 1-bromoalkane (C₈, C₁₀, C₁₂, C₁₄, C₁₆) to get 1-alkylimidazole, which was further reacted with 1,3-dichloropropan-2-ol to form the surfactant molecule, 1,1′-(propane-1,3-diyl-2-ol) bis(3-alkyl-1H-imidazol-3-ium) chloride. The structures of the five new surfactants and intermediates were characterized by ¹H-NMR, ¹³C-NMR and IR spectra. Thermal properties of the five new surfactants were studied with thermogravimetric analysis and differential scanning calorimetry, the five new surfactants showed a transition from a crystalline phase to a thermotropic liquid–crystalline phase at around ca. 100 °C, which transformed to an isotropic liquid phase at around ca. 165 °C. The five new surfactants critical micelle concentrations (CMC) in the aqueous solutions were determined by surface tension and electrical conductivity methods. The surface tension measurements provided a series of parameters, including critical micelle concentration (CMC), surface tension at the CMC (γ _CMC), adsorption efficiency  (pC ₂₀), and effectiveness of surface tension reduction (π_CMC). In addition, with application of the Gibbs adsorption isotherm, maximum surface excess concentration (Γ_max) and minimum surface area/molecule (A_min) at the air–water interface were obtained. The parameters β (degree of counterion binding to micelles), ΔG _ads ^θ (Gibbs free energy of adsorption), and ΔG _mic ^θ (Gibbs free energy change of micellization) were also derived. The results indicated that the five new Gemini surfactants exhibited very low CMC and a good efficiency in lowering the surface tension of water. The foamability and foam stability of the five new surfactants were also examined at different CMC.     

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.     

金属皂类热稳定剂对RPVC流变性能的影响

采用Brabender转矩流变仪，分析并探讨了硬酯酸钡（BaSt2）、硬酯酸铅（PbSt2）、硬酯酸钙（CaSt2）、硬酯酸锌（ZnSt2）4种硬酯酸金属皂类热稳定剂以及复配BaSt2／PbSt2热稳定剂对硬质聚氯乙烯（RPVC）流变性能的影响。结果表明，BaSt2，CaSt2能够促进RPVC的塑化，而PbSt2和ZnSt2却推迟RPVC的塑化；在复配BaSt2／PbSt2稳定剂体系中，随着BaSt2比例的增大，塑化时间缩短，但BaSt2与PbSt2按分子数1：1比率时，RPVC熔体粘度增幅较大。     

Surface Activity Properties and Aggregation Behaviors of Partially Fluorinated Gemini Surfactants in Aqueous Solution

The surface activity and aggregation behavior of partially fluorinated gemini surfactant N,N′‐bis(3‐perfluorohexyl‐2‐hydroxypropyl)‐N,N′‐dipropanesulfonylhexylenediamine (N‐6‐Sul) was studied by surface tension, resonance light scattering and fluorescence spectra measurements. The critical micelle concentration (CMC) values obtained by the three methods are in good agreement. The surface activity parameters such as the effectiveness of surface tension reduction (Π_cmc), the maximum surface excess concentration (Γ_max) and the minimum surface area per molecule (A_min) were obtained through surface tension curves. The effects of pH, inorganic salts and temperature on the surface activity were also investigated. The morphology and size of the aggregates of N‐6‐Sul were examined by transmission electron microscopy (TEM). The results show that the partially fluorinated gemini surfactant N‐6‐Sul has many advantages such as high surface activity, low CMC value, great salt tolerance and temperature resistance.     

Influence of Poloxamer 407 on Surface Properties of Aqueous Solutions of Polysorbate Surfactants

Owing to their ability to adsorb at interfaces, polysorbates have an important role in pharmaceutical formulations. Because surfactant mixtures can have improved properties, it was hypothesized in this work that introduction of poloxamer 407 to aqueous solutions of polysorbates (polysorbate 60, polysorbate 80 and polysorbate 85) might improve their surface properties. Nonideal behavior of surfactant mixtures at the air/water interface was investigated using Rosen's model and recently introduced method for the determination and quantification of nonideal behavior regarding surface tension reduction and adsorption effectiveness. Although nonideal behavior was noticed in all mixed monolayers, it was shown that the structure of the hydrophobic domain of the polysorbates and the conformation of poloxamer 407 at the interface have strong influence on the nonideality.     

歧化松香钾皂的制备与性能

以歧化松香为主要原料,在较低的温度(75～95℃)下,溶入KOH水溶液,并进行皂化反应,制备固体份质量分数45%的歧化松香钾皂。研究了反应温度、皂化时间、酸值、添加复合助剂TX-A对反应速度、去氢枞酸钾含量,以及黏度、结晶、胶凝等产品性能的影响。得出歧化松香钾皂化的较佳制备条件为:酸值12mgKOH/g、皂化时间分别为120min(未加TX-A)、98min(加TX-A)、反应温度85℃、TX-A加入量为反应物质量的0 2%。制备出的歧化松香钾皂产品,在性能上完全符合行业标准ZBB72003—84的要求,并且结晶、胶凝性质有所改善,加纳色号标准降低两个等级。     

Synthesis and Surface Properties of Anionic Gemini Surfactants having N-acylamide and Carboxylate Groups

A straightforward synthetic strategy to an anionic gemini surfactant having both N-acylamide and carboxylate groups in a molecule has been demonstrated. The surface properties of the anionic gemini surfactant, such as CMC (critical micelle concentration), C₂₀ (the concentration required to reduce the surface tension of the solvent by 20 mN/m), γ _CMC (the surface tension at the CMC), ∏ _CMC (the surface pressure at the CMC), Γ _max (the maximum surface excess concentration at the air/aqueous solution interface), A _min (the minimum area per surfactant molecule at the air/water interface), and the CMC/C₂₀ ratio (a measure of the tendency to form micelles relative to adsorbtion at the air/water interface), have been studied. The influence of the different concentrations of NaCl on the surface properties of the gemini surfactant has been discussed. The results have shown that the CMC values decreased with an increase in the concentration of NaCl indicating that the Na⁺ preferentially adsorbs onto the surface of the charged aggregate and facilitates the aggregate growth by suppressing the main impediment of electrostatic repulsion among head groups. Additionally, the values of Γ _max are always higher in salt solutions as compared to those in pure water due to their salting out effect. The larger pC₂₀ value indicates that the surfactant adsorbs more efficiently at the air/water interface and reduces surface tension more efficiently. In addition, the geminis in water show little or no break in their specific conductance versus surfactant molar concentration plots. This is attributable to protonation of the carboxylate group and strong Na⁺ release during micellization.     

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.     

Synthesis, Surface and Thermodynamic Properties of Substituted Polytriethanolamine Nonionic Surfactants

Three series of nonionic surfactants derived from polytriethanolamine containing 8, 10, and 12 units of triethanolamine were synthesized. Structural assignment of the different compounds was made on the basis of FTIR and ¹H‐NMR spectroscopic data. The surface parameters of these surfactants included critical micelle concentration (CMC), surface tension at the CMC (γ_CMC), surfactant concentration required to reduce the surface tension of the solvent by 20 mN m^?1 (pC₂₀), maximum surface excess (Γ_max), and the interfacial area occupied by the surfactant molecules (A_min) using surface tension measurements. The micellization and adsorption free energies were calculated at 25 °C.     

Effects of Surface Modifiers on Mechanical and Rheological Properties of Halogen-Free Flame Retarded Polyethylene Composites

Halogen-free flame-retarded linear low density polyethylene (LLDPE) composites were prepared in a melt process using magnesium hydroxide (MH) as a flame retardant. The effects of surface modifiers on mechanical properties and rheological behavior of the filled LLDPE have been studied. The results show that the use of surface modifiers with low molecular weight (MW) such as stearic acid or its salts, and silane coupling agents can improve greatly the elongation at break of the composites, and decrease the tensile strength in most cases. However, PE- g -DBM (LLDPE grafted with dibutyl maleate) as a polymeric compatibilizer can make the strength and elongation at break of the composites increase simultaneously. It was found from the rheological measurements that the composites containing low MW surface modifiers exhibited a lower viscosity compared with that of the composites without them, whereas the use of PE- g -DBM compatibilizer increased the viscosity of the composites. In addition, their effects on the morphological structure of the flame-retarded LLDPE composites containing surface modifiers have been investigated using scanning electron microscope (SEM).     

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.     

氟化季铵盐表面活性剂的合成及其表面活性

以三氟乙酸乙酯和N,N-二甲基乙二胺为原料,经酰化反应制得中间体NDAET;然后将NDAET与溴代十二烷发生季铵化反应得到氟化季铵盐表面活性剂N,N-二甲基-N-{2-[(2,2,2-三氟乙酰基)氨基]乙基}-1-十二烷基铵溴化物(NDAET-12)。通过FTIR、13CNMR、1HNMR对其结构进行了表征。考察了反应物物质的量比、反应时间、反应温度、溶剂用量对NDAET-12产率的影响。在单因素实验的基础上,采用正交实验对NDAET-12的合成工艺进行了优化。NDAET-12的最佳合成工艺条件为:n(NDAET)∶n(溴代十二烷)=1.0∶1.3,NDAET质量为2.76g,反应时间12h,反应温度90℃,溶剂用量为20mL。在该条件下进行平行验证实验,得到NDAET-12的平均产率为86.75%。热重分析表明,NDAET-12是一种热稳定性较好的表面活性剂。对NDAET-12的临界胶束浓度(CMC)、表面活性和乳化性能进行了测定。NDAET-12的CMC为0.8 g/L,γCMC=25.15 mN/m,表面活性较好。与十二烷基三甲基溴化铵(DTAB)和十六烷基三甲基溴化铵(CTMAB)相比,NDAET-12从乳化体系中分出10mL所需要的时间最长,为473s,具有优异的乳化性能。     

Surface and Biocidal Properties of Gemini Cationic Surfactants Based on Propoxylated 1,6-Diaminohexane and Alkyl Bromides

Two new classes of gemini cationic surfactants—hexanediyl-1,6-bis[(isopropylol) alkylammonium] dibromide {in the abbreviation form: C_nC₆C_n[iPr-OH] and C_nC₆C_n[iPr-OH]₂; alkyl: C_nH_{2n + 1} with n = 9, 10, 12 and 14}—have been synthesized by interaction of alkyl bromides with N,N′-di-(isopropylol)-1,6-diaminohexane and N,N,N′,N′-tetra-(isopropylol)-1,6-diaminohexane. The surface tension, electrical conductivity, and dynamic light scattering (DLS) techniques were used to investigate the aggregation properties of the gemini cationic surfactants in aqueous solution. The formation of critical aggregates at two concentrations in an aqueous solution from obtained gemini cationic surfactants were determined via the tensiometric method. Thus, these gemini cationic surfactants start to form aggregates at concentrations well below their critical micelle concentrations (CMC). The surface properties and the binding degree (β) of the opposite ion were tested against the length of the surfactant hydrocarbon chain and the number of the isopropylol groups in the head group. By applying the DLS technique, it was explored that how the number of isopropylol groups in gemini cationic surfactants with C₁₂H₂₅ chain affects the sizes of micelles at concentrations greater than CMC. It was discovered that the obtained gemini cationic surfactants have a biocidal character.     

Viscoelastic Properties of a Biological Hydrogel Produced from Soybean Oil

Hydrogels formed from biopolymers or natural sources have special advantages because they may have biodegradable and biocompatible properties. The viscoelastic properties of a newly developed biological hydrogel made from epoxidized soybean oil (ESO) were investigated. The material called HPESO is a hydrolytic product of polymerized ESO (PESO). HPESO exhibited viscoelastic solid or gel behavior above 2% (wt. %) concentration at room temperature and viscous liquid behavior at 55 °C. The thermal assembly disassembly reassembly function of the HPESO hydrogel was completely reversible. The viscoelastic properties of HPESO were dependent on concentration. Analysis of modulus and concentration dependence and stress relaxation measurement indicated that HPESO was a physical gel where the cross-linkers between the molecules were physical junctions. HPESO hydrogel also exhibited fast initial recovery of its viscoelastic properties after being subjected to mechanical shear disruption. The function and behavior of the HPESO hydrogel suggest that this biomaterial may be suitable for applications in drug delivery and scaffolds of bioengineering and tissue engineering. Names are necessary to report factually on available data; however, the USDA neither guarantees nor warrants the standard of the product, and the use of the name by the USDA implies no approval of the product to the exclusion of others that may also be suitable.     

Imidazolium‐Based Ionic Liquid as Modulator of Physicochemical Properties of Cationic,Anionic, Nonionic,and Gemini Surfactants

The aggregation morphology of 2 cationic surfactants (cetyldimethylethanolammonium bromide and cetyldiethylethanolammonium bromide), an anionic surfactant (sodium dodecylbenzenesulfonate), a nonionic surfactant (Triton X‐100), and 2 gemini surfactants (16‐4‐16,2Br^?[butanediyi‐1,4‐bis(dimethyldohexylammonium bromide)] and 16‐6‐16,2Br^?[hexanediyi‐1,6‐bis(dimethyldohexylammonium bromide)]) in the presence of the ionic liquid (IL) 1‐ethyl‐3‐methylimidazoliumbromide [Emim][Br] is studied using various techniques such as surface tension, conductivity, and UV–visible and fluorescence spectroscopy. Increasing the concentration of [Emim][Br] results in a decrease in the critical micelle concentration (CMC) value of the surfactants. Various interfacial properties, namely the surface excess concentration (Г_max), minimum area per molecule at the air–water interface (A_min)_, and surface pressure at the CMC (π_cmc), as well as the thermodynamic parameters such as free energy of the given air/water interface (), Gibbs free energy of micelle formation (), Gibbs free energy of micellization per alkyl tail (), Gibbs energy of transfer (), and standard free energy of adsorption () were also investigated. The aggregation number (N_agg) was determined by the fluorescence method. It was observed that N_agg decreased with increasing weight‐percent of the IL.     

Synthesis and Properties of Dissymmetric Gemini Surfactants

A series of novel dissymmetric gemini surfactants, [C _m H_2m+1COOC₂H₄(CH₃)₂N(CH₂)₃N(CH₃)₂C₂H₄OOCC _n H_2n+1]Br₂ was synthesized and symbolized as m-s–n. The Krafft temperatures and surface tension curves of the dissymmetric gemini surfactants were measured using an electrical conductivity method and a drop volume method. The low Krafft temperatures indicate very good solubility of these esterquat gemini surfactants. With the increasing numbers of carbon atoms in the hydrophobic alkyl chain, the critical micelle concentration (CMC) and the minimum surface area (A _min) decrease, and the efficiency of surface tension reduction (pc₂₀) increases. With the same numbers of carbon atoms in the hydrophobic alkyl chain, the dissymmetric gemini surfactant has a lower CMC and a smaller A _min than the corresponding symmetric gemini surfactant due to the enhanced hydrophobic interactions.     

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.     

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.