Effects of mixed surfactants on the volatilization of naphthalene from aqueous solutions

The effects of mixed anionic-nonionic surfactants, Tween40-SDS (sodium dodecyl sulfate), Tween40-SDBS (sodium dodecylbenzene sulfonate), Tween20-SDS and Tween20-SDBS, on the solubility and volatilization of naphthalene from static aqueous solutions were investigated. The experiment results indicated that mixed anionic-nonionic surfactants can solubilize naphthalene synergistically, which was resulted from the reduction in critical micelle concentration (CMC) of the mixed surfactant and the increase in micellar partition coefficient (K(mc)) of naphthalene between micelles and aqueous phase. The synergistic effects of mixed surfactants resulted in further reduction in volatilization of naphthalene than that induced by single surfactant. A positive linear correlation was found between the synergistic solubilization ratio (DeltaS) and the synergistic inhibitory capacity on naphthalene volatilization (DeltaC) in the presence of mixed surfactants. Results from this study imply that mixed surfactants can be employed in environmental remediation to formulate the needed solubility and volatilization of volatile and semivolatile compounds in aqueous solutions.     

Solubilization of DNAPLs by mixed surfactant: synergism and solubilization capacity

Efforts to remove the dense nonaqueous phase liquids (DNAPLs) in subsurface by mobilizing them face with risks of driving the contaminants deeper into aquifer zones. In this paper, a synergistical solubilization of DNAPLs by mixed nonionic and anionic surfactant, Triton X-100 (TX100) and sodium dodecylbenzene sulfonate (SDBS) in DNAPL/water systems was presented. Given 1:40 phase ratio of DNAPL:water (v/v), mixed TX100-SDBS exhibited significantly synergistical solubilization for the DNAPLs, trichloroethene (TCE), chlorobenzene (CB) and 1,2-dichlorobenzene (1,2-DCB), respectively, when the total surfactant concentration was up to 6000mg/L, i.e. the condition when solubilization by the mixture was better than those attainable with individual components by themselves. The synergistical extents depended on the initial ratios of TX100 to SDBS, the initial surfactant concentrations and the properties of DNAPLs. Given the total surfactant concentration, synergistical extents increased with the fraction of SDBS in mixed surfactant. On the contrary, did with the total surfactant concentration. The solubilization capacity by 3:1, 1:1 and 1:3 of mass ratio of TX100-SDBS were determined and compared with those by single ones. In the view of the mass solubilization ratio (SR), the mixed TX100-SDBS could solubilize more DNAPLs than single SDBS at given surfactant concentration. Reduction in partition of TX100 and synergistic solubilization were responsible for the significant solubilization extent of mixed system. The work presented here demonstrates that mixed nonionic-anionic surfactants would be preferred over the corresponding single surfactants for solubilization remediation of DNAPLs, which could decrease risks of driving the contaminants deeper into aquifers.     

Albendazole solution formulation via vesicle-to-micelle transition of phospholipid-surfactant aggregates

Objective: To reveal the physicochemical mechanisms governing the solubilization of albendazole in surfactant and phospholipid-surfactant solutions and, on this basis, to formulate clinically relevant dose of albendazole in solution suitable for parenteral delivery.

Significance: (1) A new drug delivery system for parenteral delivery of albendazole is proposed, offering high drug solubility and low toxicity of the materials used; (2) New insights on the role of surface curvature on albendazole solubilization in surfactant and surfactant-phospholipid aggregates are provided.

Methods: The effect of 17 surfactants and 6 surfactant-phospholipid mixtures on albendazole solubility was studied. The size of the colloidal aggregates was determined by light-scattering. The dilution stability of the proposed formulation was assessed by experiments with model human serum.

Results: Anionic surfactants increased very strongly drug solubility at pH?=?3 (up to 4?mg/mL) due to strong electrostatic attraction between the oppositely charged (at this pH) drug and surfactant molecules. This effect was observed with all anionic surfactants studied, including sodium dodecyl sulfate, double chain sodium dioctylsulfosuccinate (AOT), and the bile salt sodium taurodeoxycholate. The phospholipid-surfactant mixture of 40% sodium dipalmitoyl-phosphatidylglycerol +60% AOT provided highest albendazole solubilization (4.4?mg/mL), smallest colloidal aggregate size (11?nm) and was stable to dilution with model human serum at (and above) 1:12 ratio.

Conclusions: A new albendazole delivery system with high drug load and low toxicity of the materials used was developed. The high solubility of albendazole was explained with vesicle-to-micelle transition due to the larger interfacial curvature preferred for albendazole solubilization locus.     

Solubilization of pyrene by anionic-nonionic mixed surfactants

Surfactant-enhanced remediation (SER) is an effective approach for the removal of sorbed hydrophobic organic compounds from contaminated soils. The solubilization of pyrene by four anionic-nonionic mixed surfactants, sodium dodecyl sulfate (SDS) with Triton X-405 (TX405), Brij35, Brij58, and Triton X-100 (TX100), has been studied from measurements of the molar solubilization ratio (MSR), the micelle-water partition coefficient (Kmc), and the critical micelle concentration (CMC). The MSRs of pyrene in mixed surfactants are found to be larger than those predicted according to an ideal mixing rule. The mixing effect of anionic and nonionic surfactants on MSR for pyrene follows the order of SDS-TX405 > SDS-Brij35 > SDS-Brij58 > SDS-TX100 and increases with an increase in the hydrophile-lipophile balance (HLB) value of nonionic surfactant in mixed systems. In addition, the mixture of anionic and nonionic surfactants cause the Kmc value for pyrene to be greater than the ideal value in SDS-TX405 mixed system, but to be smaller than the ideal value in SDS-Brij35, SDS-Brij58, and SDS-TX100 mixed systems. Meanwhile, in the four mixed systems, the experimental CMCs are lower than the ideal CMCs at almost all mixed surfactant solution compositions. The mixing effect of anionic and nonionic surfactants on MSR for pyrene can be attributed to the conjunct or the net result of the negative deviation of the CMCs from ideal mixture and the increasing or decreasing Kmc.     

Principles for microscale separations based on redox-active surfactants and electrochemical methods.

We report principles for microscale separations based on selective solubilization and deposition of sparingly water-soluble compounds by an aqueous solution of a redox-active surfactant. The surfactant, (11-ferrocenylundecyl)trimethylammonium bromide, undergoes a reversible change in micellization upon oxidation or reduction. This change in aggregation is exploited in a general scheme in which micelles of reduced surfactant are formed and then put in contact with a mixture of hydrophobic compounds leading to selective solubilization of the compounds. The micelles are then electrochemically disrupted, leading to the selective deposition of their contents. We measured the selectivity of the solubilization and deposition processes using mixtures of two model drug-like compounds, o-tolueneazo-beta-naphthol (I) and 1-phenylazo-2-naphthylamine (II). By repeatedly solubilizing and depositing a mixture that initially contained equal mole fractions of each compound, we demonstrate formation of a product that contains 98.4% of I after six cycles. Because the aggregation states of redox-active surfactants are easily controlled within simple microfabricated structures, including structures that define small stationary volumes (e.g., wells of a microtiter plate) or flowing volumes of liquids (e.g., microfabricated channels), we believe these principles may be useful for the purification or analysis of compounds in microscale chemical process systems. When used for purification, these principles provide separation of surfactant and product.     

Micellar solubilization of poorly water-soluble drugs: effect of surfactant and solubilizate molecular structure

Objective: This study aims to clarify the role of surfactant and drug molecular structures on drug solubility in micellar surfactant solutions.

Significance: (1) Rationale for surfactant selection is provided; (2) the large data set can be used for validation of the drug solubility parameters used in oral absorption models.

Methods: Equilibrium solubility of two hydrophobic drugs and one model hydrophobic steroid in micellar solutions of 19 surfactants was measured by HPLC. The drug solubilization locus in the micelles was assessed by UV spectrometry.

Results: Danazol is solubilized much more efficiently than fenofibrate by ionic surfactants due to ion–dipole interactions between the charged surfactant head groups and the polar steroid backbone. Drug solubilization increases linearly with the increase of hydrophobic chain length for all studied surfactant types. Addition of 1–3 ethylene oxide (EO) units in the head group of dodecyl sulfate surfactants reduces significantly the solubilization of both studied drugs and decreases linearly the solubilization locus polarity of fenofibrate. The locus of fenofibrate solubilization is in the hydrophobic core of nonionic surfactant micelles and in the palisade layer of ionic surfactant micelles.

Conclusions: Highest drug solubility can be obtained by using surfactants molecules with long chain length coupled with hydrophilic head group that provides additional drug–surfactant interactions (i.e. ion–dipole) in the micelles.     

Rapid modification of montmorillonite with novel cationic Gemini surfactants and its adsorption for methyl orange

A rapid method was developed to prepare organic montmorillonite (organo-MMT) using three novel Gemini surfactants by microwave irradiation of 1 h, which was more effective than conventional heating method of 8–48 h. The structure and morphology of organo-MMTs were characterized by XRD, FT-IR, TEM and SEM. The adsorption amount of Gemini surfactants on MMT and the thermal stability of organo-MMTs were investigated by thermogravimetric analysis (TGA). The results indicated that Gemini surfactants were more efficient than cetyltrimethyl ammonium bromide in the modification of MMT, the organoclays obtained by microwave irradiation method had larger layer spacing than those from traditional heating method. And with the increase of the dosage and chain length of Gemini surfactants, the amount of the intercalary or adsorbed surfactant on the organoclay gradually increased, whereas the thermal stability weakened appropriately. Besides, the adsorption results for methyl orange indicated that all organo-MMTs displayed more excellent adsorption capacities than unmodified MMT. The amount of methyl orange adsorbed onto the organo-MMTs increased proportionately with the increase of the amount or the chain length of Gemini surfactants. This study affords a rapid and efficient method to obtain the organoclay with large interlayer distance and strong adsorption capacity.     

Effect of nonionic surfactants on the solubilization of alachlor

The ability of nonionic surfactants to solubilize the pesticide alachlor was studied. Two homologue series, octylphenol ethoxylates (Triton X-114, Triton X-100 and Triton X-102) and ethoxylated decyl alcohols (Neodol 91-5E, Neodol 91-6E and Neodol 91-8E) were used at concentrations 3 critical micelle concentration (CMC) and 6 CMC. The rate of solubilization of a sufficient quantity of alachlor (for saturation) in aqueous solution containing the micelles of nonionic surfactant was recorded. The experimental data were fitted to a first-order kinetic model. The rate constant, saturation concentration and enhancement factor were estimated for each surfactant system. The effect of surfactant structure, CMC concentration, pesticide structure and its physicochemical properties on the effectiveness of solubilization was determined. In terms of solubilization capability, the nonionic surfactants of each homologue series can be ranked as follows: Neodol 91-8E>Neodol 91-6E>Neodol 91-5E and Triton X-102>Triton X-100>Triton X-114. The more hydrophilic Neodol series was proved more efficient in alachlor solubilization than Triton series. The enhancement factor values ranged from 1.064 to 1.995 at 3 CMC and 1.320 to 2.919 at 6 CMC. The results will be used mainly for micellar-enhanced ultrafiltration since the extent of solubilization is a critical factor.     

Surfactant Solutions as Media for Dissolution Testing of A Poorly Water-Soluble Drug

The solubility of a poorly water soluble drug. 4-(4-biphenylyl)-butanol (I) was dramatically enhanced in the presence of anionic, cationic and non-ionic surfactants. Since I has no bioavailability problems on oral dosing of capsules, physiological surfactants may be involved in the solubilization of I in vivo. Thus, surfactant solutions were selected as the most relevant media for dissolution testing of capsules of I. The intrinsic dissolution of I was examined in water, sodium dodecyl sulfate (SDS), and polyoxyethylene lauryl ether (POE lauryl ether) solutions, and increases were observed. Capsule dissolution in SDS solutions was not very successful: possible reasons are discussed. POE lauryl ether was selected as the surfactant of choice. The intrinsic dissolution rates were not a linear function of concentration of POE lauryl ether in the medium. Reasons for these observations are discussed. Dissolution of capsules was examined in various concentrations of the surfactant and an optimum concentration selected.     

Effect of nonionic surfactants on biodegradation of phenanthrene by a marine bacteria of Neptunomonas naphthovorans

Biodegradation of three nonionic surfactants, Tergitol 15-S-X (X=7, 9 and 12), and their effects on the biodegradation of phenanthrene by marine bacteria, Neptunomonas naphthovorans, were studied. The experimental outcomes could be fit well with the first-order biodegradation kinetics model. It was observed that the biodegradability of these surfactants decreased with an increase in the chain length of the hydrophilic moiety of the surfactant. When surfactant concentrations initially present were less than 250mgcarbon/L, biodegradability of Tergitol 15-S-X surfactants is around 0.3. Reduced biodegradability of Tergitol 15-S-7 and Tergitol 15-S-9 was observed when their concentrations initially present were increased to 322 and 371mgcarbon/L, respectively. In general, biodegradation of phenanthrene was enhanced with increasing solubilization of phenanthrene by these surfactants. However, with the same initial concentration of phenanthrene, biodegradability of phenanthrene was found to decrease with an increase in surfactant concentration. For these three surfactants, more than 80% of the phenanthrene was degraded when surfactant concentrations initially present were 200mg/L. However, less than 30% of phenanthrene could be degraded, if initial surfactant concentrations were increased to 1000mg/L. Interestingly, the concurrent biodegradation of the surfactants reduced their effective concentrations for micelle formation and, hence, contribute to the higher bioavailability of phenanthrene by gradually releasing phenanthrene molecules into the aqueous phase.     

Effect of Cationic Surfactants on the Transdermal Permeation of Ionized Indomethacin

In an attempt to enhance the skin permeation rate of ionized indomethacin by ion-pairiig, a group of cationic surfactants were evaluated to determine their potential as counter-ions. Permeation rates through hairless rat skin were measured in vitro. The ion-pairing agents used were all quaternary ammonium compounds. Most enhanced the skin permeation of indomethacin to varying magnitudes and through different mechanisms. Some involved increased drug solubilization in the aqueous vehicle while others demonstrated permeability increase as a function of partitioning. One surfactant did not exert an apparent effect on any of the permeation parameters. Of Arquad^R 12, Arquad^R 16, Cetylpyridinium chloride^R and Benzalkonium chloride^R, only the last surfactant clearly indicated its ability to pair with indomethacin.     

Progress in synthesis and application of zwitterionic Gemini surfactants

Zwitterionic Gemini surfactants have the Gemini molecular structure in which there are both multiple lipophilic groups and multiple hydrophilic groups. However, their hydrophilic groups have different charges. Due to the special molecular structure, this kind of surfactants possesses excellent properties, including high surface activities, isoelectric point (IP), low critical micelle concentration (CMC), less toxicity, low irritating, biodegradability, bioactive, interface modification, and so on. In this review, synthetic strategies of three kinds of zwitterionic Gemini surfactants, i.e., anionic– cationic, cationic–nonionic and anionic–nonionic Gemini surfactants, are discussed, and their potential applications in life sciences, chemical industry and enhanced oil recovery (EOR) are illustrated. Their future development is also prospected.     

Study of mixed micelles and interaction parameters for polymeric nonionic and normal surfactants

Surface tension (ST) measurements were carried out on various binary mixtures of the "normal" surfactants, such as nonionic surfactant, hexaethylene glycol mono-n-dodecyl ether(C12EO6), and cationic surfactant, tetradecyltrimethylammonium bromide (TTAB), and polymeric copolymer, Pluronic F127, F127(PPO)-g-PVP, and F127(PEO)-g-PVP. In all cases mixed micellar aggregates were formed and critical micellar concentrations of binary mixtures containing different mole fractions of the surfactants were measured using surface tension measurement. In the region where mixed micelles are formed, the interaction of two "normal" surfactants and three "polymeric" nonionic surfactants showed synergistic behavior and the results were analyzed using a interaction parameter, beta, which characterized the interaction in the mixed micelle and introduced by a regular solution theory. The regular solution theory can be applied to describe the interaction between TTAB and C12EO6, and graft polymeric surfactants systems. The results discussed in this paper indicated that regular solution theory has broader extent of application.     

液膜常用表面活性剂对青霉素提取率及液膜溶胀的研究

采用以磷酸三丁酯(TBP)为流动载体,液体石蜡为膜相添加剂,煤油为膜溶剂与表面活性剂组成的W/O型乳状液膜体系提取模拟发酵液中的青霉素,考察了单一表面活性剂、混合表面活性剂对青霉素传质和液膜溶胀的影响.实验结果表明:聚胺类表面活性剂(兰113B、N205、ECA4360)对青霉素的提取率优于酯类表面活性剂(span80),且用量少、液膜溶胀率低;酯类表面活性剂与聚胺类表面活性剂不能配伍使用,聚胺类表面活性剂混合性能优于单一表面活性剂,有利于提高青霉素的传质,降低液膜溶胀.表面活性剂在液膜分离中起着极为重要的作用,直接影响着液膜的稳定性、溶胀性能及液膜的破乳.选择性能优良的表面活性剂,适宜的液膜配方和操作条件,有利于控制液膜溶胀,提高青霉素的提取率.     

Surfactant Solutions as Media for Dissolution Testing of A Poorly Water-Soluble Drug

Abstract

The solubility of a poorly water soluble drug. 4-(4-biphenylyl)-butanol (I) was dramatically enhanced in the presence of anionic, cationic and non-ionic surfactants. Since I has no bioavailability problems on oral dosing of capsules, physiological surfactants may be involved in the solubilization of I in vivo. Thus, surfactant solutions were selected as the most relevant media for dissolution testing of capsules of I. The intrinsic dissolution of I was examined in water, sodium dodecyl sulfate (SDS), and polyoxyethylene lauryl ether (POE lauryl ether) solutions, and increases were observed. Capsule dissolution in SDS solutions was not very successful: possible reasons are discussed. POE lauryl ether was selected as the surfactant of choice. The intrinsic dissolution rates were not a linear function of concentration of POE lauryl ether in the medium. Reasons for these observations are discussed. Dissolution of capsules was examined in various concentrations of the surfactant and an optimum concentration selected.     

Solubilization and mineralization of polycyclic aromatic hydrocarbons by Pseudomonas putida in the presence of surfactant

The solubilization and mineralization of polycyclic aromatic hydrocarbons (PAHs) in a soil system amended with different surfactants was examined. Mineralization experiments were conducted with the addition of [14C]pyrene. An inoculum of the PAH-degrading microorganism, Pseudomonas putida, was investigated for its sensitivity towards four non-ionic and one anionic surfactants with different polyoxyethylene (POE) chain lengths. The addition of surfactant was found to enhance the bioavailability of naphthalene, phenanthrene and pyrene with efficiencies ranging from 21.1 to 60.6%, 33.3 to 62.8% and 26.8 to 70.9%, respectively. The enhanced efficiency followed the order of Brij 30, Triton X-100, Tween 80, and Brij 35, which is correlated with the polyoxyethylene chain of the surfactants. Brij 35 and Tween 80 inhibited the growth of P. putida. However, microorganisms can utilize Triton X-100 and Brij 30 as the sole carbon and energy sources at concentrations above CMC values. In the aqueous system without the addition of surfactants, microorganisms could mineralize [14C]pyrene to 14CO(2) which corresponds to 28% of mineralization. The addition of surfactants decreased the mineralization rate of pyrene. Also, the fraction of the micellar-phase pyrene that can be directly biodegraded decreased as the concentration of micelle increases. However, the mineralization rate can be enhanced by the amendment of Brij 30 when soil was applied to the cultures. This suggests that biodegradable surfactants can be applicable for increasing the bioavailability and mineralization of PAHs in soil systems.     

蒙脱土插层纳米复合材料改性涂料研究

采用双子季铵盐（GeminiC1）6表面活性剂和十六烷基三甲基溴化铵（CTAB）表面活性剂分别与钠基蒙脱土（Na-MMT）进行阳离子交换后,制备了新的有机蒙脱土（GeminiC16-MMT和CTAB-MMT）,通过X射线衍射（XRD）、透射电镜（TEM）等对有机蒙脱土进行表征并对其分散性做了测试。又用蒙脱土插层纳米复合材料改性水性涂料,并进行了性能测试表征,结果显示,经改性涂料的性能均有不同程度的提高。     

Mathematical modeling of pH-surfactant-mediated solubilization of nimesulide

Aim: The equilibrium-based mathematical model was used to describe the pH-surfactant-mediated solubilization of weakly acidic electrolyte, nimesulide, in buffer solutions. This model assumed that the total drug solubility could be expressed as a sum of the solubilities of four different species: unionized and ionized form in solution and their corresponding micellar forms. Sucrose-laurate, new synthetic surfactant, and polysorbate 80 were investigated for their benefits in the testing of poorly soluble acidic model drug. Method: Two sets of solubility data, determined at pH values 4.5 and 9.0 in media containing different surfactant concentrations, were used to calculate solubilization slopes and corresponding micellar equilibrium constants for the unionized (Kn) and ionized (K_i) drug. These values were used to estimate drug solubilization in media considered to represent physiologically relevant conditions. Results: Predicted solubility values were in good agreement with the experimental data, suggesting that the impact of pH and surfactant on nimesulide solubility could be well characterized by the equilibrium model described in this article. Conclusions: Obtained results indicated that the extent of solubilization was significantly dependent on the surfactant used.     

MALDI-TOF mass spectrometry of insoluble giant polycyclic aromatic hydrocarbons by a new method of sample preparation

The insolubility of giant polycyclic aromatic hydrocarbons (PAHs) prevents their characterization by conventional analytical methods, which require a solubilization of the analyte. Laser desorption mass spectrometry may be used to analyze insoluble samples but is limited to relatively low molecular weights (approximately 2000), in the case of PAHs. To overcome this limitation, we applied MALDI-TOF mass spectrometry. Since MALDI sample preparation also requires solubility of analyte and matrix molecules, the sample preparation needed modification. The giant PAHs (>2000 Da) were investigated after using a new sample preparation, consisting of mechanically mixing analyte and matrix without any solubilization procedures. This solvent-free process allows insoluble compounds to be characterized. Furthermore, new organic molecules can be used as a matrix. Indeed, 7,7,8,8-tetracyanoquinodimethane, a new matrix with promising properties, has proven to be particularly suitable for the measurement of PAHs. Thanks to the successful characterization with MALDI-TOF mass spectrometry, the chemical design of giant PAHs, which was hindered until now for a lack of analytical methods, can now continue to develop.     

聚乙二醇对无机盐的胶束增溶作用及在溶胶配制中的应用*

在有机体系溶胶中掺杂无机盐通常十分困难,原因在于有机溶剂和无机盐之间的不相容性。本文提出一种有效的新方法解决了这一困难。往溶胶中加入聚乙二醇表面活性剂,利用聚乙二醇的胶束增溶作用增大了无机盐在溶胶中的溶解度,从而有利于配制出均匀掺杂的溶胶。表面活性剂的胶束增溶作用对于用溶胶凝胶法合成复合陶瓷具有重要意义,应用前景广阔。