AFM study on the adsorption and aggregation behavior of dissolved humic substances on mica

Humic substances (HS) are a category of naturally occurring, biogenic, heterogeneous organic materials found in or extracted from soils, sediments, and natu- ral waters that can generally be characterized as being yellow-to-black in color, of highly variable relative molecular masses, and refractory[1,2]. Derived from a variety of organic precursors (plant biopolymers such as lignin etc.), plant residues and animal debris via both transformation and synthesis processes[3] under the profound ge…     

Disruption of aggregates of a Zn2+-complex of a schiff base in water by surfactants: Insights from fluorescence spectroscopy in ensemble and single molecule levels

Schiff bases and their metal ion complexes have potential biological applications. It is important to study their interactions with biomimemtic assemblies in order to design such applications. To this effect, the nature and interaction between the aggregates of an organic fluorophore (Znsalampy) and surfactants viz. sodium dodecyl sulfate (SDS) and cetyl trimethyl ammonium bromide (CTAB) have been monitored using bulk macroscopic techniques like steady state and time resolved fluorescence as well as single molecule techniques like Fluorescence Correlation Spectroscopy (FCS). The presence of more than one kind of aggregates is observed in neat aqueous solutions is confirmed by the complementary techniques. The more rigid aggregates are found to be less prone to disruption by surfactants. SDS is found to be significantly more effective than CTAB in breaking the aggregates of Znsalampy.     

Binding of ionic surfactants to purified humic acid

The binding of organic contaminants to dissolved humic acids reduces the free concentration of the contaminants in the environment and also may cause changes to the solution properties of humic acids. Surfactants are a special class of contaminants that are introduced into the environment either through wastewater or by site-specific contamination. The amphiphilic nature of both surfactants and humic acids can easily lead to their mutual attraction and consequently affect the solution behavior of the humics. Binding of an anionic surfactant (sodium dodecyl sulfate, SDS) and two cationic surfactants (dodecyl- and cetylpyridinium chloride, DPC and CPC) to purified Aldrich humic acid (PAHA) is studied at pH values of 5, 7, and 10 in solutions with a 0.025 M ionic strength (I). Monomer concentrations of the surfactants are measured with a surfactant-selective electrode. At I = 0.025 M, no significant binding is observed between the anionic surfactant (SDS) and PAHA, whereas the two cationic surfactants (DPC, CPC) bind strongly to PAHA over the pH range investigated. The binding is due both to electrostatic and hydrophobic attraction. The initial affinity increases with increasing pH (i.e., negative charge of PAHA) and tail length of the surfactant. Binding reaches a pseudo-plateau value (2-5 mmol/g) when the charge associated with PAHA is neutralized by that of the bound surfactant molecules. The pseudo-plateau values for DPC and CPC are very similar and depend on the solution pH. The cationic surfactant-PAHA complexes precipitate when the charge neutralization point is reached. This occurs at approximately 10% of the critical micelle concentration or CMC. This type of phase separation commonly occurs during surfactant binding to oppositely charged polyelectrolytes. For CPC, the precipitation is complete, but in the case of DPC, a noticeable fraction of PAHA remains in solution. At very low CPC concentrations (less than 0.1% of the CMC), CPC binding to PAHA is cooperative. The investigated range of concentrations for DPC was too limited to reach a similar conclusion. The results of this study demonstrate that the fate of humic acids will be strongly affected by the presence of low cationic surfactant concentrations in aqueous environmental systems.     

THE EFFECTS OF MIXED MICELLES OF SURFACTANTS ON POLYMERIZATION OF ACRYLAMIDE

The polymerization of acrylamide in mixed micellar solutions of surfactants, initiated by NaHSO₃ has been studied at 20 and 3Q° C with time variable method of thermokinetics for 1. 5-order reaction. The results indicate that the mixed micellar systems of cationic or anionic with zwitterionic surfactants (SLS/ CTAB, SLS/ TTAB, SLS/ SDS) and cationic with nonionic surfactants (Brij 357sol; CTAB, Bri-J35/TTAB, Brij35/ DTAB) have catalytic effect on the polymerization in the order, at 20° C. SLS/ SDS SLS/ TTAB SLS/ CTAB Brij35/ CTAB at 30° C SLS/ SDS SLS/ TTAB≈ / CTAB Bri-j35/ DTAB= sBrij35/ TTAB as Brij35/ CTAB, while Brij35/ SDS mixed micellar system has inhibition. These effects are attributed to the effect of the Stern layer of mixed micelles on the step of initiator (HSOT) to form free radical.     

阳离子表面活性剂对有机颜料艳红6B光催化降解的影响

 研究了阳离子表面活性剂四丁基溴化铵(TBAB)和十六烷基三甲基溴化铵(CTAB)对TiO2光催化降解艳红6B(R6B)的影响,讨论了表面活性剂与R6B的相互作用,给出了二者与TiO2之间的吸附模型. 结果表明,相同条件下,阳离子表面活性剂的加入可增加R6B的降解褪色速率,但表面活性剂自身并不降解. 在强酸(pH=3.00)和强碱(pH=12.60)条件下,R6B的降解褪色速率较快. pH值相同时,体系中TBAB的浓度变化对R6B降解褪色速率的影响不大,而CTAB浓度的变化对R6B降解褪色速率的影响较为明显,CTAB浓度为0.4 g/L时R6B的降解褪色速率最快.     

Photocatalytic degradation of hydrocarbons by bentonite and TiO2 in aqueous suspensions containing surfactants

Organic substances (toluene, asphaltene dissolved in toluene) poorly soluble in water were solubilized by sodium dodecylsulfate (SDS) and the organic pollutants were mineralized together with the surfactants in diluted TiO₂ suspension by UV light. In concentrated aqueous suspension, crude oil was photodegraded on the surface of Na-bentonite and the photocatalyst TiO₂. Experiments have been carried out with Na-bentonite contaminated with crude oil mixed in a ratio of 1:1 with TiO₂ as well. The photooxidation processes were followed by total organic carbon content (TOC) and diffuse reflection infrared spectroscopy (DRIFT) measurements.     

Spectrophotometric study of interaction and solubilization of procaine hydrochloride in micellar systems

The interaction of Procaine hydrochloride (PC) with cationic, anionic and non-ionic surfactants; cetyltrimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS) and triton X-100, were investigated. The effect of ionic and non-ionic micelles on solubilization of Procaine in aqueous micellar solution of SDS, CTAB and triton X-100 were studied at pH 6.8 and 29°C using absorption spectrophotometry. By using pseudo-phase model, the partition coefficient between the bulk water and micelles, K_x, was calculated. The results showed that the micelles of CTAB enhanced the solubility of Procaine higher than SDS micelles (K_x = 96 and 166 for SDS and CTAB micelles, respectively) but triton X-100 did not enhanced the solubility of drug because of weak interaction with Procaine. From the resulting binding constant for Procaine-ionic surfactants interactions (K_b = 175 and 128 for SDS and CTAB surfactants, respectively), it was concluded that both electrostatic and hydrophobic interactions affect the interaction of surfactants with cationic procaine. Electrostatic interactions have a great role in the binding and consequently distribution of Procaine in micelle/water phases. These interactions for anionic surfactant (SDS) are higher than for cationic surfactant (CTAB). Gibbs free energy of binding and distribution of procaine between the bulk water and studied surfactant micelles were calculated.      

Mixed cationic/anionic surfactants for semipermanent wall coatings in capillary electrophoresis

Mixtures of the cationic surfactant cetyltrimethylammonium bromide (CTAB) with the anionic surfactant sodium dodecyl sulfate (SDS) form more stable coatings in fused-silica capillaries than CTAB alone. The reversed electroosmotic flow (EOF) generated by CTAB/SDS mixtures remains stable for over 80 min after removal of the surfactants from the buffer. Enhanced stability (relative to CTAB alone) was found even when the ratio of SDS to CTAB was as low as 1%. This greater coating stability is attributed to the structural transition from adsorbed micelle to bilayer, which is induced by addition of SDS. Separation of a mixture of basic proteins yielded efficiencies of 364 000-562 000 plates/m and recoveries ranging from 85% to 98%. Migration time reproducibility was less than 0.9% relative standard deviation (RSD) from run to run and less than 2.6% RSD from day to day.     

Liquid chromatography-(tandem) mass spectrometry of selected emerging pollutants (steroid sex hormones,drugs and alkylphenolic surfactants) in the aquatic environment

Among the various compounds considered as emerging pollutants, alkylphenolic surfactants, steroid sex hormones, and pharmaceuticals are of particular concern, both because of the volume of these substances used and because of their activity as endocrine disruptors or as causative agents of bacterial resistance, as is the case of antibiotics. Today, the technique of choice for analysis of these groups of substances is liquid-chromatography coupled to mass spectrometry (LC–MS) and tandem mass spectrometry (LC–MS–MS). In the last decades, this technique has experienced an impressive progress that has made possible the analysis of many environmental pollutants in a faster, more convenient, and more sensitive way, and, in some cases, the analysis of compounds that could not be determined before. This article reviews the LC–MS and LC–MS–MS methods published so far for the determination of alkylphenolic surfactants, steroid sex hormones and drugs in the aquatic environment. Practical considerations with regards to the analysis of these groups of substances by using different mass spectrometers (single quadrupole, ion trap and triple quadrupole instruments, etc.), interfaces and ionization and monitoring modes, are presented. Sample preparation aspects, with special focus on the application of advanced techniques, such as immunosorbents, restricted access materials and molecular imprinted materials, for extraction/purification of aquatic environmental samples and extracts are also discussed.     

Surfactant displacement of human serum albumin adsorbed on loosely packed self-assembled monolayers: cetyltrimethylammonium bromide versus sodium dodecyl sulfate

The surfactants sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB) displace human serum albumin (HSA) from loosely packed self-assembled monolayers (SAM) of hydrophobic alkyl chains by different means. Removal of HSA is of interest because previous work has suggested that the adsorption of HSA to such loosely packed SAMs may be sufficiently tenacious to offer opportunities for surface passivation. While HSA remains on the surface after exposure to SDS and rinsing, no protein remains after exposure to CTAB and rinsing. X-ray reflectivity and X-ray photoelectron spectroscopy measurements indicate that CTAB molecules remain interdigitated in the loosely packed SAM after rinsing, suggesting that CTAB is more effective in removing the HSA because it interacts more strongly with the SAM.     

Adsorption behavior of hydrophobin and hydrophobin/surfactant mixtures at the air-water interface

The adsorption of the surface-active protein hydrophobin, HFBII, and the competitive adsorption of HFBII with the cationic, anionic, and nonionic surfactants hexadecyltrimethylammonium bromide, CTAB, sodium dodecyl sulfate, SDS, and hexaethylene monododecyl ether, C(12)E(6), has been studied using neutron reflectivity, NR. HFBII adsorbs strongly at the air-water interface to form a dense monolayer ～30 ? thick, with a mean area per molecule of ～400 ?(2) and a volume fraction of ～0.7, for concentrations greater than 0.01 g/L, and the adsorption is independent of the solution pH. In competition with the conventional surfactants CTAB, SDS, and C(12)E(6) at pH 7, the HFBII adsorption totally dominates the surface for surfactant concentrations less than the critical micellar concentration, cmc. Above the cmc of the conventional surfactants, HFBII is displaced by the surfactant (CTAB, SDS, or C(12)E(6)). For C(12)E(6) this displacement is only partial, and some HFBII remains at the surface for concentrations greater than the C(12)E(6) cmc. At low pH (pH 3) the patterns of adsorption for HFBII/SDS and HFBII/C(12)E(6) are different. At concentrations just below the surfactant cmc there is now mixed HFBII/surfactant adsorption for both SDS and C(12)E(6). For the HFBII/SDS mixture the structure of the adsorbed layer is more complex in the region immediately below the SDS cmc, resulting from the HFBII/SDS complex formation at the interface.     

吲哚方酸菁染料在表面活性剂水溶液中的光降解

考察了4种含有不同N位取代基的对称吲哚方酸菁染料在阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)、阴离子表面活性剂十二烷基硫酸钠(SDS)和非离子表面活性剂曲拉通(TX-100)水溶液中的光降解行为,结果表明,表面活性剂对染料分子具有保护作用,其影响大小为CTAB>TX-100>SDS,分子中有羧基的染料受影响程度最大。在表面活性剂浓度较低时,染料光降解程度随着表面活性剂浓度的增加而增加,但形成胶束后,染料的光降解程度则随着表面活性剂浓度的升高而降低。     

Determination of Bismuth by Adsorptive Stripping Voltammetry Using Aluminum Oxide for Elimination of Environmental Sample Matrix Interferences

The aim of this work was to find a fast new and simple method for efficient elimination of negative influence of humic substances and synthetic surfactants in the voltammetric determination of bismuth. The negative influence of the organic matrix present in environmental water samples due to their adsorption on aluminum oxide was successfully evaluated. The organic compounds such as humic substances and surface active compounds were removed by adsorption on the surface of aluminum oxide from the water samples. The application of this method was the recovery of Bi(III) from spiked water samples.     

Self-motion of a camphanic acid disk on water with different types of surfactants

Control of the self-motion of a camphanic acid disk on water was investigated upon the addition of different kinds of surfactants (Triton X-100 and Brij58 as neutral surfactants, cetyltrimethylammonium bromide (CTAB) as a cationic surfactant, and sodium dodecyl sulfate (SDS) as an anionic surfactant) to the water phase. With an increase in the concentration of surfactant, continuous motion changed to no motion via intermittent motion (repetition between motion and rest), and the concentration regions of these motions were different among these surfactants. Although the concentration regions of these motions were determined by the surface tension for neutral surfactants, they were different than those for CTAB and SDS. These characteristics of self-motion are discussed in relation to the surface tension, depending on the concentration of individual surfactants, and the hydrophilic effect of the surfactants.     

Interaction between silicates and ionic surfactants in dilute solution

Understanding the interaction between silicate ions and surfactants is critical for the design and development of mesoporous siliceous materials. We examined the interaction between sodium silicate ions and three different cationic surfactants [namely, cetyltrimethylammonium bromide (CTAB), tetradecyltrimethylammonium bromide (TTAB), and dodecyltrimethylammonium bromide (DTAB)] and an anionic surfactant [sodium dodecyl sulfate (SDS)] in dilute solution at room temperature. From the combination of several techniques, such as conductometric and potentiometric titrations, dynamic light scattering, and isothermal titration calorimetry, the phase behavior of the sodium silicate and CTAB system was determined. We observed that the aggregation behavior of the silicate-CTAB system is similar to that of a polymer-surfactant system. The formation of the silicate-CTAB complex is induced by the adsorption of SiOH and SiO- groups, aided by CTAB unimers. The electrostatic attraction and hydrophobic interaction are the dominant forces controlling the formation of silicate-CTAB complexes. When these complexes are saturated with CTAB unimers, free CTAB micelles are then produced. TEM micrographs revealed that a stable Si-O-Si network is absent within the silicate-CTAB complexes, and surprisingly, stable silicate-CTAB complexes with ordered structure were observed. The present finding is important for understanding the interaction between silicate and surfactant in the synthesis of mesoporous structure in the dilute solution regime.     

Crystal modification of calcium sulfate dihydrate in the presence of some surface-active agents

The effect of surface-active agents (surfactants), as additives, on the crystallization of gypsum was studied under conditions of the simulated dihydrate process of phosphoric acid production. Calcium hydrogen phosphate and sulfuric acid were mixed with dilute phosphoric acid at 80 degrees C, and the turbidity of the reaction mixture was measured at different time periods to determine the induction time of gypsum crystal formation. Two types of surfactants, namely, cetyltrimethylammonium bromide (CTAB) as a cationic surfactant and sodium dodecyl sulfate (SDS) as an anionic surfactant were added to investigate their effects on the crystallization of gypsum. Addition of CTAB decreased the induction time and increased the growth efficiency, while addition of SDS increased the induction time and decreased the growth efficiency compared with the baseline (without additives). The surface energy increased with CTAB and decreased with SDS compared with the baseline. The percentage of fine crystals decreased in the presence of CTAB and increased in the presence of SDS compared with the baseline. Gypsum morphology changed from needle-like in the absence of additives to tabular in the presence of CTAB.     

Polymethylmethacrylate derivatives Eudragit E100 and L100: Interactions and complexation with surfactants

Precipitation or coprecipitation of polyelectrolytes has been largely investigated. However, the precipitation of polyelectrolytes via addition of charged and non‐charged surfactants has not been systematically studied and reported. Consequently, the aim of this work is to investigate the effect of different surfactants (anionic, cationic, non‐charged and zwitterionic) on the precipitation of cationic and anionic polymethylmethacrylate polymers (Eudragit). The surfactants effect has been investigated as a function of their concentration. Special attention has been dedicated to the CMC range and to the colloidal characterization of the formed dispersions. Moreover, the effect of salt (NaCl) and pH was also addressed. It is pointed out that non‐ionic and zwitterionic surfactants do not interact with charged Eudragit E100 and L100. For oppositely charged Eudragit E100/SDS and Eudragit L100/CTAB, precipitation occurs, and the obtained dispersions have been characterized in terms of particle size distribution and zeta potential. It was established that the binding of SDS molecules to Eudragit E100 polymer chains is made through the negative charges of the surfactant heads under the CMC value whereas binding of CTAB to Eudragit L100 chains is made at a CTAB concentration 5 times above its CMC. For Eudragit E100/SDS system, a more acidic medium induces aggregation. A same result was observed for the Eudragit L100/CTAB at a more basic pH. Moreover, it was observed that increasing salt concentration (higher than 100 mM) led to aggregation as generally observed for polycations/anionic surfactant systems.     

Analysis and fate of surfactants in sludge and sludge-amended soils

Surfactants are among the most prevalent organic pollutants of anthropogenic origin with the potential to enter the environment through the discharge of wastewater and sewage sludge. We give an overview of analytical methods currently in use for the determination of different classes of surfactants in sewage sludge and soil. The main focus is on the application of liquid chromatography-mass spectrometry (LC-MS) and gas chromatography-mass spectrometry (GC-MS), discussing various aspects of these two techniques, including sample preparation. We give an overview of data on the occurrence of sludge and sludge-amended soils, and we draw conclusions about the fate of surfactants and their metabolites in sludge-amended soils. Finally, we briefly discuss the current European legislation relating to the use of sludge in agriculture.     

卵清蛋白与离子型表面活性剂的相互作用

本文通过荧光光谱法、紫外-可见吸收光谱法和透射电镜并结合电导率测定分别研究了水中卵清蛋白与阴离子表面活性剂十二烷基硫酸钠（SDS）和阳离子表面活性剂十二烷基三甲基溴化铵（DTAB）和十六烷基三甲基溴化铵（CTAB）之间的相互作用。研究结果表明卵清蛋白可以增加SDS和CTAB的临界胶束浓度,但对DTAB的临界胶束浓度没有影响。阴离子表面活性剂可以使卵清蛋白构象完全伸展,而阳离子表面活性剂却不具备此种作用。表面活性剂单体与卵清蛋白的相互作用强于表面活性剂胶束与卵清蛋白的相互作用。     

Assessment of the relations between the spectroscopic characteristics of soils and their ability to adsorb organic pollutants

The aim of this research was to study the way the humus content of the soils affects the adsorption of particular organic pollutants. We used five different media during the experiments: two different soils (sandy soil, coherent soil), humic acid extracts extracted from these soils, and a commercially available humic acid product. We studied the adsorbed amount of the given compounds at the particular media, the role of humic materials in the observed adsorption ratios, and whether the co-existence of the different compound changes the adsorption–desorption conditions.The inorganic components of the soils play an important role also in the absorption of the apolar compounds, and as the polarity (or polarizability) of the organic compound increases, the humic materials of the soil, or rather their polar functional groups take the dominant role in the absorption of the pollutant. The absorption and desorption of three apolar compounds were practically not influenced by the presence of other pollutants in the soil, and this phenomenon was also independent from the extracting agent. However, in the case of polar diuron, the presence of other pollutants can result in decrease of mobility.