双子型阴离子表面活性剂的合成及浮选性能

分别以辛酰氯、癸酰氯、十二酰氯为原料,经加成、酰化及皂化等反应合成了3种双子型阴离子表面活性剂。产物结构经IR、1HNMR和13CNMR等波谱测试技术确定。25℃时测定了表面活性参数,结果表明随分子中疏水链增长,临界胶束浓度及表面张力均降低。目标化合物能一定程度增强油酸对胶磷矿中白云石的浮选能力。     

Equilibrium and dynamic surface tension properties of partially fluorinated quaternary ammonium salt gemini surfactants

The equilibrium and dynamic surface tension properties of a partially fluorinated quaternary ammonium salt gemini surfactant 1,2-bis[dimethyl-(3-perfluoroalkyl-2-hydroxypropyl)ammonium]ethane bromide (C(n)(F)C3-2-C3C(n)F, where n represents fluorocarbon chain lengths of 4, 6, and 8) were investigated, and the effects of the fluorocarbon chain length and the number of chains on them were discussed. The plot of the logarithm of the critical micelle concentration (cmc) against the fluorocarbon chain length for C(n)(F)C3-2-C3C(n)F showed a linear decrease with an increase in chain length. On the basis of the slope of this plot, it was found that the variation in cmc with respect to the chain length is large for fluorinated gemini surfactants. The surface tension at the cmc decreased significantly; this surface tension value is lower than that of conventional fluorinated monomeric surfactants. In particular, the lowest value was 13.7 mN m(-1) for n = 8. Furthermore, it was confirmed that the kinetics of adsorption at the interface decrease with an increase in the fluorocarbon chain length and the concentration.     

Synthesis and surface properties of anionic gemini surfactants with amide groups

Novel anionic gemini surfactants, 1,2-bis(N-beta-carboxypropanoyl-N-alkylamino)ethane (2CnenAm; n is hydrocarbon chain length of 6, 8, 10, 12, or 14), with two hydrocarbon chains, two carboxylate groups, and two amide groups, were synthesized by three-step reactions. Their solution properties were characterized by equilibrium and dynamic surface tension, steady-state fluorescence spectroscopy of pyrene, and dynamic light-scattering techniques. The surface tension measurements of 2CnenAm give low critical micelle concentrations (cmc), great efficiency in lowering the surface tension, and strong adsorption at air/water interface. Gemini surfactants behave normally with the logarithm of cmc decrease linearly with the chain length. In addition, adsorption and micellization behavior of 2CnenAm was estimated by parameter of pC20, cmc/C20, and standard free energy (DeltaG(0)mic and DeltaG(0)ads); they are significantly influenced by hydrocarbon chain length, and the adsorption is promoted more than the micellization as chain length becomes longer. The results of dynamic light-scattering and fluorescence quenching indicate that small micelles of 2CnenAm are observed at the concentrations above the cmc, and further large particles are also seen. Further, from the dynamic surface tension measurements, it is found that the shorter hydrocarbon chain length of 2CnenAm, the faster the rate of decrease of surface tension.     

Synthesis and properties of thioether spacer containing gemini imidazolium surfactants

Twelve new gemini imidazolium surfactants have been synthesized, having dodecyl, tetradecyl, hexadecyl, and octadecyl chain lengths and three different spacers (i.e., -S-(CH(2))(n)-S-), where n = 2, 3, and 4 and their surface properties have been evaluated by surface tension and conductivity methods. The thermal degradation of these new gemini surfactants was determined by thermogravimetric analysis (TGA). These surfactants have low cmc values as compared to other categories of gemini cationic surfactants and exhibit peculiarities at sufficiently low concentration because they were able to form premicellar aggregates over a wide range of concentration below their cmc values. The DNA binding affinity of these gemini surfactants determined by agarose gel electrophoresis and ethidium bromide exclusion experiments established their strong interaction with DNA, thereby protecting it against enzymatic degradation.     

Gemini imidazolium surfactants: synthesis and their biophysiochemical study

New gemini imidazolium surfactants 9-13 have been synthesized by a regioselective epoxy ring-opening reaction under solvent-free conditions. The surface properties of these new gemini surfactants were evaluated by surface tension and conductivity measurements. These surfactants have been found to have low critical micelle concentration (cmc) values as compared to other categories of gemini cationic surfactants and also showed the tendency to form premicellar aggregates in solution at sufficiently low concentration below their cmc values. The thermal degradation of these surfactants was determined by thermograviometry analysis (TGA). These new cationic surfactants have a good DNA binding capability as determined by agarose gel electrophoresis and ethidium bromide exclusion experiments. They have also been found to have low cytotoxicity by MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assay on the C6 glioma cell line.     

Structural effects on surface and micellar properties of alkanediyl-alpha, omega-bis(sodium N-acyl-beta-alaninate) gemini surfactants

A study of the equilibrium surface properties (in water and in the presence of 0.01 M NaCl) of a novel series of anionic gemini surfactants, alkanediyl-alpha,omega-bis(sodium N-acyl-beta-alaninates), is described. Parameters studied include cmc (critical micelle concentration), C20 (required to reduce the surface tension of the solvent by 20 mN/m), gamma(cmc) (the surface tension at the cmc), Gamma(max) (the maximum surface excess concentration at the air/aqueous solution interface), Amin (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 adsorb at the air/water interface). The geminis with a spacer consisting of two methylene groups show premicellar self-aggregation, both in water and in 0.01 M NaCl, when the N-acyl group contains more than 12 carbon atoms; geminis with a spacer consisting of four methylene groups show no premicellar aggregation even when the N-acyl group contains 16 carbon atoms. For the acyl chain lengths where premicellar aggregation does not occur, the values of the cmc of the geminis with a two-methylene spacer are lower than those for the corresponding analogous geminis with a four-methylene spacer. The premicellar formation for the geminis with a two-methylene spacer is due to the short-chain linkage. The geminis show little or no break in their specific conductance-surfactant molar concentration plots and an increase in the pH at the cmc. This is attributed to protonation of the carboxylate group and strong Na+ release during micellization.     

Effect of hydrocarbon structure of the headgroup on the thermodynamic properties of micellization of cationic gemini surfactants: an electrical conductivity study

A series of cationic gemini surfactants butanediyl-1,4-bis(dodecyldialkylammonium bromide), C(12)H(25)N(+)(C(m)H(2)(m)(+1))(2)C(4)H(8)N(+)(C(m)H(2)(m)(+1))(2)C(12)H(25)·2Br(-), where m=1, 2, 3, 4, referred to as C(12)C(4)C(12)(Me), C(12)C(4)C(12)(Et), C(12)C(4)C(12)(Pr), and C(12)C(4)C(12)(Bu), respectively, were synthesized, and their thermodynamic properties of micellization were studied by electrical conductivity measurements. There existed a minimum critical micelle concentration (cmc) in the curve of cmc versus temperature, and the temperature of the minimum of cmc (T(min)) increased with increasing the headgroup alkyl chain length. The values of log (cmc) depended linearly on carbon number of the alkyl chains, but that was not true for the carbon number of the headgroup substituents. The temperature dependence of cmc and degree of counterion association (β) were used to calculate the Gibbs free energy (Δ(mic)G°), enthalpies (Δ(mic)H°) and entropies (Δ(mic)S°) of micelle formation for these gemini surfactants, and well correlated enthalpy-entropy compensation was observed. The analyses showed C(12)C(4)C(12)(Me) and C(12)C(4)C(12)(Et) behaved similarly in terms of thermodynamics of micellization, but they behaved differently from C(12)C(4)C(12)(Pr) and C(12)C(4)C(12)(Bu), which could be ascribed to the hydrophobicity and the location of the headgroup alkyl chains in the aggregates. These initial results indicate the headgroup alkyl chain plays an important role in influencing the thermodynamic properties of gemini surfactants.     

Asp-Gly based peptides confined at the surface of cationic gemini surfactant aggregates

Cationic gemini surfactants complexed with anionic oligoglycine-aspartate (called gemini peptides hereafter) were synthesized, and their aggregation behaviors were studied. The effects of the hydrophobic chain length (C10-C22) and the length of the oligoglycine (0-4) were investigated, and it was clearly shown by critical micellar concentration, Krafft temperature, and isothermal surface pressure measurements that the hydrophobic effect and interpeptidic interaction influence the aggregation behavior in a cooperative manner. Below their Krafft temperatures, some of them formed both hydro- and organogels with three-dimensional networks and the Fourier transform infrared measurements show the presence of interpeptidic hydrogen bonds.     

Mixed micellar properties of cationic trimeric-type quaternary ammonium salts and anionic sodium n-octyl sulfate surfactants

The properties of quaternary ammonium salt-type cationic trimeric surfactants (m-2-m-2-m, m represents the carbon atom number in alkyl chain lengths of 8, 10, and 12) and oppositely charged anionic monomeric surfactant, sodium n-octyl sulfate (SOS), were characterized by employing several techniques such as static surface tension, fluorescence spectroscopy, and dynamic light-scattering measurements. The critical micelle concentrations (cmc) of m-2-m-2-m were much lower than those of the corresponding dimeric and monomeric surfactants, and decreased with increasing chain length. The addition of SOS to m-2-m-2-m solutions resulted in a further decrease of the cmc. The mixed surfactants showed higher efficiencies in lowering the surface tension than the individual surfactants. The fluorescence measurements suggested the formation of mixed micelles with a hydrophobic environment in the solutions even at lower concentrations. The dynamic light-scattering study indicated the presence of two different kinds of aggregates with different hydrodynamic diameters. The larger one was attributed to the mixed micelle of m-2-m-2-m and SOS. These results indicated a decline of the electrostatic repulsion between cationic head groups through the incorporation of anionic surfactant into the mixed surfactants.     

Synthesis and properties of a novel class of gemini pyridinium surfactants

A novel class of gemini pyridinium surfactants with a four-methylene spacer group was synthesized, and their surface-active properties and interactions with polyacrylamide (PAM) were evaluated by surface tension, fluorescence, and viscosity measurements. A comparison between the gemini pyridinium surfactants and their corresponding monomers was also made. The cmc's of gemini pyridinium surfactants are much lower than those of the corresponding monomeric surfactants. The C20 value is about one order of magnitude lower than that of corresponding monomers, and the longer the hydrophobic chains of the surfactants, the lower the cmc value. Surface tension measurements of the surfactant-PAM mixed systems show that the critical aggregation concentration (cac) value is much lower than the cmc value of the surfactant system alone. Viscosity measurements of the surfactant-PAM mixed systems show that the relative viscosity of the surfactant-PAM system decreased with increasing concentration of surfactant. Additionally, fluorescence measurements of the surfactant-PAM mixed system suggest the formation of surfactant-polymer aggregates, and the gemini pyridinium surfactant with longer hydrophobic chains have a stronger interaction with PAM, owing to the stronger hydrophobic interaction.     

Synthesis and Properties of Aromatic Side Chained N‐Acyltaurate Surfactants

A series of anionic N‐acyltaurate surfactants, side chain containing aromatic nucleus (abbreviated as SAATT), were synthesized via Williamson reaction, hydrolyzation, and acylation. Krafft temperatures and surface properties of these surfactants at 30°C, that is, critical micelle concentration, cmc, surface excess concentration, Γ_max, surface area demand per molecule, A _min, efficiency in surface tension reduction, pC₂₀, effectiveness in surface tension reduction, π_cmc, and cmc/C₂₀ parameter were determined. It was shown that these surfactants exhibit good solubility which was confirmed by measuring Krafft temperature. The cmc of SAATT was much smaller than that of conventional surfactants with similar effective carbon numbers, and shifted to lower concentration with increasing hydrocarbon chain length. In addition, the γ_cmc decreased with decrease in Γ_max. The pC₂₀ and the cmc/C₂₀ got larger with the increase in hydrocarbon chain length. From the fluorescence intensity ratios of I ₁ (373 nm) and I ₃ (384 nm) using pyrene as a probe, it was indicated that the molecules of SAATT formed loose micelles with a broad size distribution.     

两相催化体系中双子表面活性剂对1-十二烯氢甲酰化反应的助催化作用

合成了几种具有刚性连接基团的双子表面活性剂,研究了它们在Rh-TPPTS体系中催化长链烯烃氢甲酰化反应中的助催化作用.结果表明,在水/有机两相催化体系中,新型双子表面活性剂的助催化作用比单链表面活性剂CTAB更好,在较低的表面活性剂浓度下能得到较高的反应转化率.这归因于此类表面活性剂有较低的cmc,降低界面张力的能力和对1-十二烯的增溶能力比CTAB更强.     

Enhanced interfacial properties of novel amino acid-derived surfactants: Effects of headgroup chemistry and of alkyl chain length and unsaturation

Amino acid-derived surfactants have increasingly become a viable biofriendly alternative to petrochemically based amphiphiles as speciality surfactants. Herein, the Krafft temperatures and critical micelle concentrations (cmc) of three series of novel amino acid-derived surfactants have been determined by differential scanning microcalorimetry and surface tension measurements, respectively. The compounds comprise cationic molecules based on serine and tyrosine headgroups and anionic ones based on 4-hydroxyproline headgroups, with varying chain lengths. A linear dependence of the logarithm of cmc on chain length is found for all series, and in comparison to conventional ionic surfactants of equal chain length, the new amphiphiles present lower cmc and lower surface tension at the cmc. These observations highlight their enhanced interfacial performance. For the 18-carbon serine-derived surfactant the effects of counterion change and of the presence of a cis-double bond in the alkyl chain have also been investigated. The overall results are discussed in terms of headgroup and alkyl chain effects on micellization, in the light of available data for conventional surfactants and other types of amino acid-based amphiphiles reported in the literature.     

Mixed micelle formation among anionic gemini surfactant (212) and its monomer (SDMA) with conventional surfactants (C12E5 and C12E8) in brine solution at pH 11

The micellization of anionic gemini surfactant, N,N'-ethylene(bis(sodium N-dodecanoyl-beta-alaninate)) (212), and its monomer, N-dodecanoyl-N-methyl alaninate (SDMA), and polyethoxylated nonionic surfactants, C(12)E(5) and C(12)E(8), has been studied tensiometrically in pure and mixed states in an aqueous solution of 0.1 M NaCl at pH 11 to determine physicochemical properties such as critical micellar concentration (cmc), surface tension at the cmc (gamma(cmc)), maximum surface excess (Gamma(max)) and minimum area per surfactant molecule at the air/water interface (A(min)). The theories of Rosen, Rubingh, Motomura, Maeda, and Nagarajan have been applied to investigate the interaction between those surfactants at the interface and in the micellar solution, the composition of the aggregates formed, the theoretical cmc in pure and mixed states, and the structural parameters as proposed by Tanford and Israelachvili. Various thermodynamic parameters (free energy of micellization and interfacial adsorption) have been calculated with the help of regular solution theory and the pseudophase model for micellization.     

Star-shaped trimeric quaternary ammonium bromide surfactants: adsorption and aggregation properties

Novel star-shaped trimeric surfactants consisting of three quaternary ammonium surfactants linked to a tris(2-aminoethyl)amine core were synthesized. Each ammonium had two methyls and a straight alkyl chain of 8, 10, 12, or 14 carbons. The adsorption and aggregation properties of these tris(N-alkyl-N,N-dimethyl-2-ammoniumethyl)amine bromides (3C(n)trisQ, in which n represents alkyl chain carbon number) were characterized by equilibrium and dynamic surface tension, rheology, small-angle neutron scattering (SANS), and cryogenic transmission electron microscopy (cryo-TEM) techniques. 3C(n)trisQ showed critical micelle concentrations (CMC) 1 order of magnitude lower than that of the corresponding gemini surfactants with an ethylene spacer and the corresponding monomeric surfactants. The logarithm of the CMC decreased linearly with increasing hydrocarbon chain length for 3C(n)trisQ. The slope of the line, which is well-known as Klevens equation, was larger than those of the monomeric and gemini surfactants; however, considering the total carbon number in the chains, the slope was shallower than the monomeric and was close to the gemini. Through the results such as surface tensions at the CMC (32-34 mN m(-1)) and the parameters of standard free energy, CMC/C(20) and pC(20), it was found that 3C(n)trisQ could adsorb densely at the air/water interface despite the strong electrostatic repulsion between multiple quaternary ammonium headgroups. Moreover, dynamic surface tension measurements showed that the kinetics of adsorption for 3C(n)trisQ to the air/water interface was slow because of their bulky structures. Furthermore, the results of rheology, SANS, and cryo-TEM determined that 3C(n)trisQ with n = 10 and 12 formed ellipsoidal micelles at low concentrations in solution and the structures transformed to threadlike micelles with very few branches for n = 12 as the concentration increased, but for n = 14 threadlike micelles formed at relatively low concentrations.     

C12-s-C12·2Br与低碳醇混合水溶液胶团化行为的温度效应和焓/熵补偿

季铵盐Gemini表面活性剂C12-s-C12·2Br(s=2,3,4,6)与丙醇、丁醇、戊醇、己醇混合水溶液的In(cmc)随温度升高而逐渐增大.计算所得热力学数据表明,C12-s-C12·2Br与醇混合胶团化过程服从熵驱动机理,也出现了焓/熵补偿现象.随着温度上升,熵驱动力增大,在指定温度时,醇分子烷烃链上碳原子数n增大使△Gm0值减小,胶团结构更加稳定;而增加s使值增大,胶团稳定性下降.     

Supra-long chain surfactants with double or triple quaternary ammonium headgroups

Novel supra-long chain surfactants with double or triple quaternary ammonium salts (C(n)-2Am, C(n)-3Am, in which n represents a hydrocarbon chain length of 18, 20, and 22) were synthesized, and electrical conductivity and surface tension were used to characterize their properties depending on both the hydrocarbon chain length and number of hydrophilic groups. The Krafft temperatures decreased remarkably with an increase in the quaternary ammonium headgroups, resulting in a high solubility in water. The critical micelle concentration (cmc) increased with an increase in the number of quaternary ammonium moieties in the hydrophilic group, and the difference in the cmc was smaller for C(n)-2Am and C(n)-3Am than for C(n)-2Am and C(n)-Am of alkyltrimethylammonium bromide. The surface tension at the cmc was approximately 45 and 48 mN m(-1) for C(n)-2Am and C(n)-3Am with n=18-22, respectively. This indicated that the supra-long chain surfactants could not efficiently adsorb at the air/water interface and orient by themselves, as is known for conventional surfactants.     

荧光探针法研究新型Gemini表面活性剂在水溶液中的聚集行为

以芘为荧光探针、二苯酮为猝灭剂,用稳态荧光探针法测定了新型Gemini表面活性剂的临界胶团浓度(CMC)、胶团聚集数(N_agg)及胶团微极性.研究了Gemini表面活性剂结构和氯化钠浓度对CMC、N_agg、胶团微极性的影响.结果表明,新型Gemini表面活性剂的CMC比常规表面活性剂的CMC低1—2个数量级.当疏水基碳原子数增加时,CMC依次降低,N_agg增大,胶团微极性减小.当氯化钠浓度增大时,N_agg增大,胶团微极性减小.     

Effects of organic salt additives on the behavior of dimeric ("gemini") surfactants in aqueous solution

The effects of a series of aromatic anions, so-called hydrotropes, on characteristic solution properties of a family of ammonium gemini surfactants with dodecyl chains were explored. The stoichiometric addition of the organic salts to the geminis can result in clear solutions or in phase separation/precipitation, depending on the detailed nature of the added counterions and on the spacer group of the gemini surfactant. Many organic anions induce synergistic effects, strongly reducing the critical micellization concentration (cmc) and the surface tension at the cmc. Furthermore, a number of combinations of organic anions and geminis exhibit thickening of their aqueous solutions. The effects of the added salts are strongly enhanced for the gemini surfactants compared to the monomeric analogue N-dodecyl-N,N,N-trimethylammonium chloride. Even anions such as benzoate may be effective for thickening, and viscoelastic solutions can be obtained with salicylate despite the relatively short alkyl chains.     

Alkanediyl-alpha,omega-bis(dimethylalkylammonium bromide) surfactants 10. Behavior in aqueous solution at concentrations below the critical micellization concentration: an electrical conductivity study

Ion pairing and premicellar association have been often invoked to explain results obtained in studies of aqueous solutions of ionic dimeric surfactants (gemini surfactants), mainly by means of surface tension and electrical conductivity, at concentrations below the critical micellization concentration (cmc). The present work was undertaken in an attempt to find out under which conditions these effects come into play. For this purpose the electrical conductivity of solutions of many dimeric surfactants of the type spacer-alpha,omega-bis(alkyldimethylammonium bromide) have been measured. The alkyl chain contained m=10-18 carbon atoms. The spacer group was either an alkanediyl with s carbon atoms (m-s-m surfactants) or a xylylene m-xylyl-m surfactants). The results show that ion pairing occurs in solutions of m-s-m dimers with m< or =10, mostly as a result of their high cmc values. The results for 12-s-12 dimers with s< or =10 and for 12-xylyl-12 showed no evidence of either ion pairing or premicellar association. Premicellar association was present for 12-s-12 dimers with s> or =12, for m-8-m dimers with m> or =14, and for 16-xylyl-16. It showed through a positive curvature of the specific conductivity versus concentration plot and the presence of a maximum in the equivalent conductivity vs (concentration)(0.5) plot at concentrations below the cmc. The free energy associated with the premicellar association of m-8-m dimers has been estimated from the available cmc and micelle ionization degree data.