Surfactant Sodium Dodecyl Sulfate Molecules Research Articles

Gas-liquid interface properties of fluorocarbon and hydrocarbon surfactants and their mixed foams: Molecular dynamics simulations and experimental studies

This paper focuses on the gas-liquid interface characteristics of short-chain fluorocarbon surfactant FS-50 and hydrocarbon surfactant sodium dodecyl sulfate (SDS) and their mixed systems. The foam properties of SDS, FS-50, and their mixed solutions were experimentally determined. Then, based on the molecular dynamics simulation method, the interaction mechanism of surfactant molecules at the gas-liquid interface was simulated and analyzed by constructing a foam-liquid membrane system containing surfactant molecules and water molecules. The experimental results show that FS-50 can effectively enhance the foam stability when the concentration is lower than 0.16 wt% and the mixing ratio with SDS is not more than 1:1; the simulation results show that FS-50 can change the arrangement of SDS molecules at the gas-liquid interface. Simultaneously, there is a competitive adsorption phenomenon between FS-50 and SDS at the gas-liquid interface. The low mixing ratio FS-50 can increase the thickness of the gas-liquid interface of the mixed system and the ability of SDS to form hydrogen bonds with water, enhance the water-locking ability of SDS, and further improve the stability of the foam liquid film. The interaction mechanism between short-chain fluorocarbons and SDS surfactants at the gas-liquid interface was revealed by simulation, which provided theoretical guidance for optimizing the performance of the foam liquid film.

Self-assembly of mixed surfactants sodium dodecylsulfate and polyethylene glycol dodecyl ether in aqueous solutions

The thermodynamic behavior of mixed systems containing the anionic surfactant sodium dodecyl sulfate (SDS) and the nonionic surfactant polyethylene glycol dodecyl ether (Brij L4) in aqueous solutions was investigated. Electrical conductivity and interfacial tension measurements were employed to investigate the concentration-dependent properties of these surfactant mixtures. Two main experiments were conducted: i) constant ratio experiment: the overall surfactant concentration was varied while maintaining a fixed ratio between SDS and Brij L4. It was shown that the critical micelle concentration (CMC) determined from electrical conductivity measurements does not indicate the formation of the first mixed micelles as observed using tensiometry, but the point from which the adsorption of counterions by the existing micelles became important. By using the Regular Solution Theory (RST), it was found that the interaction between SDS and Brij L4 is synergistic, driven by dipole-ion interactions of the hydrophilic regions of the two surfactants. ii) Fixed SDS concentration while increase the Brij L4 concentration: the resulting electrical conductivity exhibited non-trivial behavior which complexity arose from simultaneous phenomena of incorporation of free SDS molecules into the micelles as Brij L4 concentration increased, leading to a decrease in electrical conductivity; liberation of some adsorbed counterions from the mixed micelles to the solution, which increases the conductivity and increase of viscosity due to Brij L4 further addition that leads to a sequential decrease in electrical conductivity.

Surfactant-based supramolecular dye assembly: A highly selective and economically viable platform for quantification of heparin antidote

Herein, we have employed a supramolecular assembly of a cationic dye, LDS-698 and a common surfactant sodium dodecyl sulfate (SDS) as a turn-on fluorescent sensor for protamine (Pr) detection. Addition of cationic Pr to the solution of dye-surfactant complex brings negatively charged SDS molecules together through strong electrostatic interaction, assisting aggregation of SDS way before its critical micellar concentration (CMC). These aggregates encapsulate the dye molecules within their hydrophobic region, arresting non-radiative decay channels of the excited dye. Thus, the LDS-698•SDS assembly displays substantial enhancement in fluorescence intensity that follows a nice linear trend with Pr concentration, providing limit of detection (LOD) for Pr as low as 3.84(±0.11) nM in buffer, 124.4(±6.7) nM in 1% human serum and 28.3(±0.5) nM in 100% human urine. Furthermore, high selectivity, low background signal, large stokes shift, and emission in the biologically favorable deep-red region make the studied assembly a promising platform for Pr sensing. As of our knowledge it is the first ever Pr sensory platform, using a very common surfactant (SDS), which is economically affordable and very easily available in the market. This innovative approach can replace the expensive, exotic and specialized chemicals considered for the purpose and thus showcase its potential in practical applications.

Electrophoretic coalescence behavior of oil droplets in oil-in-water emulsions containing SDS under DC electric field: A molecular dynamics study

The presence of oil droplets in oil-in-water (O/W) emulsions seriously affects the efficiency of wastewater purification, and the appropriate addition of surfactants can effectively improve the demulsification process. In this paper, the electrophoretic coalescence behavior of oil droplets containing anionic surfactant sodium dodecyl sulfate (SDS) under a direct current (DC) electric field was studied based on molecular dynamics (MD) simulations, and four typical stages of oil droplet migration coalescence were defined. The weak interactions between SDS and water and between SDS and n-hexane are mainly van der Waals interactions, while a small number of hydrogen bonds are formed between SDS and water and between water molecules internally. With the increase of electric field strength (E), the deformation of oil droplets after aggregation increases, and the contact angle with the electrode plate becomes smaller. The interfacial tension between oil and water decreases and then increases with increasing surfactant concentration, reaching a minimum value of 32.52 mN/m when the number of SDS molecules (n) around each oil droplet is 55. When E = 1.2 V/nm and n = 55, the coalescence time of oil droplets reaches the minimum value of 2.425 ns. The migration rate of oil droplet far from the anode is greater than that of oil droplet near the anode, which is due to the larger combined forces on the former. The results reveal the microscopic mechanism of oil droplet migration and coalescence under the coupling effect of DC electric field and anionic surfactant, which could provide theoretical guidance for the improvement of oily wastewater purification process.

Effect of mixed surfactants on foam stabilization: A molecular dynamics simulation

Mixed surfactants have antagonistic or synergistic effects on the air/liquid interface of foams, representing two opposite interactions about destroying or stabilizing foams. In this paper, mixed surfactant systems containing non-ionic surfactant polyoxyethylene alkyl ether (AEO) and anionic surfactant sodium dodecyl sulfate (SDS) were discussed by molecular dynamics simulation to study the mechanism of decreasing stability of SDS foam after AEO was added. The results showed that with the addition of AEO, the interaction between SDS molecules is weakened, and the thickness of hydrated shell around the polar head of SDS decreases. In order to simulate the process of foam drainage and rupture, steered molecular dynamics (SMD) containing two external forces on the foam film was performed. One is about the z-axis vertical external force, representing the stability of SDS hydrated layer at the interface; the other is about the external force in horizontal direction, representing the rupture process of the liquid film. The simulated results showed that the higher the concentration of AEO in the mixed surfactant interface layer, the smaller the external force to destroy the foam film interface. In addition, the free energy change of AEO molecules from the water phase through the SDS layer to the air phase further showed that the addition of AEO can reduce the stability of SDS foam films and play a defoaming role in the studied system. The simulated conclusions were consistent with the experimental results about the decreasing stability of SDS foam after AEO was added.

Physical Insight into the Conditions Required in the Solid-Phase Molecular Self-Assembly of SDS Revealed by Coarse-Grained Molecular Dynamics Simulation.

Molecular self-assembled materials have attracted considerable interest in recent years. As part of the efforts to overcome the shortcoming that the solution-based methods were hardly applicable in preparing bulk macroscopic molecular self-assemblies, Yan [ CCS Chem. 2020, 2, 98-106] developed a strategy of solid-phase molecular self-assembly (SPMSA) that allows scaling up the generation of massive supramolecular films. It is highly desired to understand the physical insight into the SPMSA at a molecular level. Here, in combination with the experimental study, we report molecular dynamics (MD) simulations on the SPMSA of the surfactant sodium dodecyl sulfate (SDS) using a coarse-grained method with the Martini force field model. The MD simulations clearly manifest that a small amount of water is required to endow the SDS molecules with sufficient mobility to self-assemble, and the smaller size of the preassembled SDS particles favors their further fusion into mesophases by reducing the total surface Gibbs free energy, while the smaller interparticle distance decreases the time for the particle fusion. The simulation results agree well with the conditions required in the experiment, confirming that SMPSA is a free-energy-favored process leading to bulk self-assembled materials.

Exploration of the Adsorption Kinetics of Surfactants at the Water-Oil Interface via Grand-Canonical Molecular Dynamics Simulations.

It is well-known that surfactants tend to aggregate into clusters or micelles in aqueous solutions due to their special structures, and it is difficult for the surfactant molecules involved in the aggregation to move spontaneously to the oil-water interface. In this article, we developed a new grand-canonical molecular dynamics (GCMD) model to predict the saturated adsorption amount of surfactant with constant concentration of surfactant molecules in the bulk phase, which can prevent surfactants aggregating in the bulk phase and get the atomic details of the interfacial structural change with increase of the adsorption amount through a single GCMD run. The adsorption of anionic surfactant sodium dodecyl sulfate (SDS) at the heptane-water interface was studied to validate the model. The saturated adsorption amount obtained from the GCMD simulation is consistent with the experimental results. The adsorption kinetics of SDS molecules during the simulation can be divided into three stages: linear adsorption stage, transition adsorption stage, and dynamic equilibrium stage. We also carried out equilibrium molecular dynamics (EMD) simulations to compare with GCMD simulation. This GCMD model can effectively reduce the simulation time with correct prediction of the interfacial saturation adsorption. We believe the GCMD method could be especially helpful for the computational study of surfactant adsorption under complex environments or emulsion systems with the adsorption of multiple types of surfactants.

Novel molecular insight into the discrepant distributions for ionic surfactants in light oil/water and heavy oil/water systems

Surfactant exhibits great displacement efficiency for the light oil (aliphatic and aromatic hydrocarbons) reservoir, whereas the heavy components (resins and asphaltenes) in crude oil could seriously affect the interfacial activity of surfactants. Then two simulation systems (light oil/water and heavy oil/water systems) were established and the distribution behaviors of the anionic surfactant sodium dodecyl sulfate (SDS) in above two systems were investigated by molecular dynamics (MD) simulation. The simulation results revealed that some SDS molecules could stay in the heavy oil phase but not in the light oil phase. The potential of mean force (PMF) of two systems were calculated to further probe the Gibbs free energy change in the movement process of SDS molecules form water phase to oil phase. The interaction mechanisms of water/surfactant/oil in the movement process were illustrated by the corresponding system configurations and reduced density gradient (RDG) method. The water molecules in hydration shell could be pulled into heavy oil phase coupled with SDS molecules and connect with SDS and asphaltene molecules to fabricate the SDS-Water-Asphaltenes (S-W-A) ternary structure via hydrogen bonds. Furthermore, the interaction energy calculation directly demonstrated the formation of S-W-A structure should be responsible for the discrepant distributions of surfactants in light oil/water and heavy oil/water systems.

Ubiquitin forms conventional decorated micelle structures with sodium dodecyl sulfate at saturation

The anionic surfactant sodium dodecyl sulfate (SDS) interacts strongly with most globular proteins and denatures and unfolds them. While scattering studies using X-rays and neutrons have shown that this denaturation generally leads to protein-decorated SDS micelles, a different SDS-decorated polypeptide model has recently been suggested for complexes between SDS and Ubiquitin (UBI), in which individual SDS molecules are distributed on a partially stretched protein. To resolve this apparent discrepancy, we have investigated the SDS-UBI system by a number of complementary techniques. Small-angle X-ray scattering (SAXS) provides the overall structure of the SDS-UBI complexes, Tyr fluorescence and circular dichroism follow changes in tertiary and secondary structure, and isothermal titration calorimetry determines the stoichiometries of complexes and the amount of free SDS as a function of [SDS]. At low [SDS], UBI preserves its folded structure but dimerizes to a small extent. At 4 SDS per UBI, a complex is formed with two UBI and a small shared SDS cluster with 8 SDS molecules. In these complexes UBI preserves most of its native fold. At 10–12 SDS per UBI, which remains below the critical micelle concentration under our conditions, UBI-covered SDS micelles form with four UBIs around a core of 40 SDSs. This implies a protein-assisted micellization and an associated unfolding of UBI involving a change from mainly β-strands to mainly α-helical secondary structure. As [SDS] is increased, the complex gradually changes so that finally only one UBI covers one micelle with a similar number of SDS molecules at SDS saturation. Thus, we conclude that SDS unfolds UBI by mechanisms very similar to those observed for other globular proteins, leading to a protein-decorated SDS micelle rather than an SDS-decorated unfolded polypeptide chain.

Multi-Step Unfolding and Rearrangement of α-Lactalbumin by SDS Revealed by Stopped-Flow SAXS.

Interactions between proteins and surfactants are both of fundamental interest and relevant for applications in food, cosmetics and detergency. The anionic surfactant sodium dodecyl sulfate (SDS) denatures essentially all proteins. Denaturation typically involves a number of distinct steps where growing numbers of SDS molecules bind to the protein, as seen in multidisciplinary approaches combining several complementary techniques. We adopt this approach to study the SDS-induced unfolding of Ca2+-depleted α-lactalbumin (aLA), a protein particularly sensitive toward denaturation by surfactants. By combining stopped-flow mixing of protein and surfactant solutions with stopped-flow synchrotron small-angle X-ray scattering (SAXS), circular dichroism (CD) and Trp fluorescence, together with information from previous calorimetric studies, we construct a detailed picture of the unfolding process at the level of both protein and surfactant. A protein-surfactant complex is formed within the dead time of mixing (2.5 ms). Initially a cluster of SDS molecules binds asymmetrically, i.e., to one side of the protein, after which aLA redistributes around the SDS cluster. This occurs in two kinetic steps where the complex grows in number of both SDS and protein molecules, concomitant with protein unfolding. During these steps, the core-shell complex undergoes changes in shell thickness as well as core shape and radius. The entire process is very sensitive to SDS concentration and completes within 10 s at an SDS:aLA ratio of 9, decreasing to 0.2 s at 60 SDS:aLA. The number of aLA molecules per SDS complex drops from 1.9 to 1.0 over this range of ratios. While both CD and Trp kinetics reveal a fast and a slow conformational transition, only the slow transition is observed by SAXS, indicating that the protein-SDS complex (which is monitored by SAXS) adjusts to the presence of the unfolded protein. We attribute the rapid unfolding of aLA to its predominantly α-helical structure, which persists in SDS (albeit as isolated helices), enabling aLA to unfold without undergoing major secondary structural changes unlike β-sheet rich proteins. Nevertheless, the overall unfolding steps are broadly similar to those of the more β-rich protein β-lactoglobulin, suggesting that this unfolding model is representative of the general process of SDS-unfolding of proteins.

Effect of hydrophobically modified SiO2 nanoparticles on the stability of water-based SDS foam

In the present study, SiO2 nanoparticles were first hydrophobically modified and then added into anionic surfactant sodium dodecyl sulfate (SDS) stabilized water-based foam to improve the foam stability. The foam stability was experimentally evaluated by measuring surface tension, Zeta potential and half-life of the foam. The foam stabilizing mechanism was also studied from a micro perspective by molecular dynamics simulation through analyzing the equilibration configuration and MSD curve of both SDS surfactant and water molecules. The results show that foam exhibits an optimal stability when SiO2 concentration is 0.35 wt% under a specific surfactant concentration (0.5 wt%) in this work. The addition of SiO2 nanoparticles with suitable concentration could improve the adsorption between SDS molecules and nanoparticles, thus limiting the movement of SDS and restricting the movement of surrounding water molecules, which is beneficial to enhance the foam stability.

Ecotoxicity and interacting mechanism of anionic surfactant sodium dodecyl sulfate (SDS) and its mixtures with nonionic surfactant fatty alcohol-polyoxyethlene ether (AEO)

This paper reports the proportion-dependent toxicity of binary surfactant mixtures containing anionic sodium dodecyl sulfate (SDS) and nonionic fatty alcohol-polyoxyethlene ether (AEO) toward Photobacterium phosphoreum. The crucial role of toxicity interactions was elucidated by spectroscopic probing the refolding of the unfolded bovine serum albumin (BSA) induced by SDS and theoretical calculating the interaction parameter of mixed surfactants based on Rubingh’s model from the critical micelle concentrations. The SDS/AEO mixtures can be divided into two groups based on the toxicity response to the proportion of AEO in the mixtures: Group I contained low mass proportions of AEO, that is, SDS:AEO = 4:1, 3:1; Group II featured high AEO proportions, that is, SDS:AEO = 3:2, 1:1, 2:3, 1:4. The toxicity of SDS/AEO mixtures decreased with the enhanced proportion of AEO in Group I and then fluctuated slightly when the AEO proportion increased to that of Group II. The mixture with the mass ratio of 1:1 showed a slightly higher toxicity than the others in Group II. Scanning electron microscopy (SEM) images illustrated that the addition of AEO hindered the action of SDS against the cell membrane. Fluorescence measurement indicated that AEO could extract SDS molecules embedded in the BSA matrix, except for those bound to the highly active sites of BSA, and refold stepwise the unfolded protein. The results were in excellent analogy to the proportion-dependent toxicity of SDS/AEO mixture, indicating the formation of mixed micelles playing a key role. The interaction parameter further revealed that antagonism led to the mixture with equal mass ratio (1:1) showing higher toxicity than other mass ratios in Group II. These results can be useful for compounding SDS/AEO mixtures in application efficiently and eco-friendly.

CO2/N2 switchable aqueous foam stabilized by SDS/C12A surfactants: Experimental and molecular simulation studies

A novel CO2/N2 switchable aqueous foam was developed using a CO2-responsive surfactant N,N-dimethyl-N-dodecyl amine (C12A) and a conventional surfactant sodium dodecyl sulfate (SDS). The performance and mechanism of this switchable foam were studied by both experiment and molecular simulation methods. Experimental results demonstrate that the foam stabilized by SDS/C12A surfactants has better stability and water carrying capacity than single C12A foam. The foam could be rapidly switched between stable and unstable states at ambient temperature with CO2 or N2 as the triggers. Simulation results shows that when CO2 was introduced, most of SDS and C12A molecules aggregated in the water phase, instead of adsorbing at the air-water interface to stabilize the foam films. The strong electrostatic attraction between protonated C12A and SDS molecules could account for the aggregation. Due to the presence of limited surfactants located at the air-water interface after introducing CO2, the foam bursts quickly.

PH-switchable and CO2-switchable viscoelastic fluids based on a pseudo-hydrophobically associating water-soluble polymer

The non-hydrophobically associating water-soluble polymer (DPAM) of acrylamide (AM) and dimethylamino propyl methacrylamide (DMAPMA) was synthesized. Then pH-switchable and CO2‑switchable viscoelastic liquids based on DPAM and anionic surfactant sodium dodecyl sulfate (SDS)(referred to as DPAM-SDS) were developed. When minor HCl aqueous solution was added into the DPAM and SDS aqueous mixture or CO2 was bubbled into it, the tertiary amine groups of DPAM were protonated to form quaternary ammonium groups, some of which in the same quaternary ammonium groups of DPAM “bridged” some SDS through noncovalent electrostatic attraction, behaving like a pseudo-hydrophobically associating water-soluble polymer and forming viscoelastic fluids as checked through environmental scanning electron microscope(ESEM) and rheology. Upon removing of CO2 or back of pH by minor NaOH aqueous solution, the quaternary ammonium species of DPAM were deprotonated back to tertiary amine groups, separating the pseudo-hydrophobically associating water-soluble polymer back to DPAM and SDS molecules, which resulted in forming low-viscosity water solution. The switchable viscoelastic conversion can be repeated.

Coarse-Grain Molecular Dynamics Simulations To Investigate the Bulk Viscosity and Critical Micelle Concentration of the Ionic Surfactant Sodium Dodecyl Sulfate (SDS) in Aqueous Solution.

The first critical micelle concentration (CMC) of the ionic surfactant sodium dodecyl sulfate (SDS) in diluted aqueous solution has been determined at room temperature from the investigation of the bulk viscosity, at several concentrations of SDS, by means of coarse-grain molecular dynamics simulations. The coarse-grained model molecules at the mesoscale level are adopted. The bulk viscosity of SDS was calculated at several millimolar concentrations of SDS in water using the MARTINI force field by means of NVT shear Mesocite molecular dynamics. The definition of each bead in the MARTINI force field is established, as well as their radius, volume, and mass. The effect of the size of the simulation box on the obtained CMC has been investigated, as well as the effect of the number of SDS molecules, in the simulations, on the formation of aggregates. The CMC, which was obtained from a graph of the calculated viscosities versus concentration, is in good agreement with the reported experimental data and does not depend on the size of the box used in the simulation. The formation of a spherical micelle-like aggregate is observed, where the dodecyl sulfate tails point inward and the heads point outward the aggregation micelle, in accordance with experimental observations. The advantage of using coarse-grain molecular dynamics is the possibility of treating explicitly charged beads, applying a shear flow for viscosity calculation, and processing much larger spatial and temporal scales than atomistic molecular dynamics can. Furthermore, the CMC of SDS obtained with the coarse-grained model is in much better agreement with the experimental value than the value obtained with atomistic simulations.

Effects of nonionic surfactant and salts on the interactions between oppositely charged star-shaped copolymer and ionic surfactant in aqueous solutions

The interaction between star-shaped copolymer poly(2-(dimethylamino)ethyl methacrylate-b-2-(2-methoxyethoxy)ethyl methacrylate) (CDPDPM) and anionic surfactant sodium dodecyl sulfate (SDS) in aqueous solutions are investigated by using fluorescence and dynamic light scattering (DLS) techniques. The effects of nonionic surfactant dodecyl β-D-maltopyranoside (C12G2) and salts including inorganic salt ammonium bromide (NH4Br) and organic salt tetra-n-butylammonium bromide (Bu4NBr) on the interaction between CDPDPM and SDS have been explored systematically. The results have suggested that SDS molecules can bind on CDPDPM by electrostatic interaction between the positively charged CDPDPM and negatively charged SDS and thus weaken the binding ability of CDPDPM to water molecules. CDPDPM exhibits temperature-responsive aggregation behavior in aqueous solution gradually with the increase of SDS concentration and the lower critical solution temperature (LCST) decreases correspondingly. The introduction of nonionic surfactant C12G2 changes the interaction between CDPDPM and SDS significantly by participate the formation of complexes and the stability of the CDPDPM/SDS complexes declines leading to the chance of forming larger complexes is deprived at higher temperature. The addition of NH4Br to the CDPDPM/SDS system can retard the binding of SDS on the polymer chains because of electrostatic shielding. Correspondingly, LCST is higher and the formed aggregates are smaller. For CDPDPM/Bu4NBr/SDS system, the phenomenon is similar to that of the CDPDPM/C12G2/SDS system. This should be attributed to the nature of Bu4N+, possesses not only positive charges but also certain hydrophobicity, and thus Bu4N+ has the ability to participate and facilitate the formation of SDS micelles. Obviously, the LCST of the mixed system can be tailored by adjusting the system composition on purpose.

Molecular dynamics simulations of aggregation behavior of sodium dodecyl sulfate on SiO2 and CaCO3 surfaces

Molecular dynamics simulations were carried out to investigate the aggregation behavior of anionic surfactant sodium dodecyl sulfate (SDS) on the surfaces of SiO2 and CaCO3. The results indicate that SDS molecules formed a spherical micelle structure near the SiO2 surface; moreover, there were more head groups near the SiO2 surface. However, they could form a self‐assemble film on the CaCO3 surface. The self‐assemble film of SDS on the CaCO3 surface was more stable than that on the SiO2 surface. Our simulation results have a certain significance to understand the aggregation behavior of SDS on different surfaces on molecular level.

Interaction of Sodium Dodecyl Sulfate with Lipid Monolayer Studied by Sum-Frequency Generation Spectroscopy at Air–Water Interface

We employed vibrational sum-frequency generation (VSFG) spectroscopy to obtain molecular-level understanding of interaction of anionic surfactant sodium dodecyl sulfate (SDS), in low bulk concentration at the micromolar level, with lipid monolayer zwitterionic 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) at the air–water interface. These results are different from those reported at higher bulk concentration of SDS at millimolar level. At very low concentration neither DPPC nor SDS produces any VSFG signal in the CH stretch region in the water subphase, but with the same concentration DPPC produces typical VSFG spectra at the SDS subphase due to interaction between these two molecules. The interaction leads to polar ordering of DPPC molecules with enhancement of VSFG intensity in the CH vibrational region of the hydrophobic tails. The interaction between the lipid and SDS molecules is influenced by concentrations of both lipid and SDS. Hydrophobic interactions between long alkyl chains of SDS and DPP...

Complexation of a Globular Protein, β-Lactoglobulin, with an Anionic Surfactant in Aqueous Solution.

The complexation of a globular protein, β-lactoglobulin (BLG), and an anionic surfactant sodium dodecyl sulfate (SDS) in aqueous media was investigated using capillary zone electrophoresis, electrophoretic, static, and dynamic light scattering, and small-angle X-ray scattering in a considerably high protein concentration range (0.27 mM < CP < 3 mM). On increasing the molar concentration CR of the surfactant, cooperative binding of SDS to BLG starts at CR/CP ≈ 1; the BLG-SDS complex consists mainly of the BLG dimer and approximately 20 SDS molecules, where BLG takes a compact conformation similar to that of the native BLG up to CR/CP ≈ 20. At CR/CP higher than 30, the BLG dimer in the BLG-SDS complex dissociates into a unimer, but the dissociated BLG unimer still takes a compact conformation at least at 30 < CR/CP < 65.

Spectroscopic and Calorimetric Studies of Molecular Recognitions in a Dendrimer-Surfactant Complex.

Molecular recognitions, causing supramolecular complex formation between a hyperbranched polymer molecule (polyamidoamine (PAMAM) dendrimer generation 3) with oppositely charged surfactant sodium dodecyl sulfate (SDS) in aqueous solution, were studied by using various spectroscopic techniques and calorimetric titration of heat change measurements. Spectroscopic measurements were performed using dynamic Stokes shift (DSS), rotational anisotropy decay, and translational diffusion of a fluorescent probe molecule coumarin 153 (C153) noncovalently attached to the dendrimer-surfactant complex. All these studies unanimously confirm that the critical aggregation concentration (CAC) of SDS falls to ∼0.8 mM (from its critical micelle concentration (CMC) ∼ 8 mM) in the presence of ∼0.2 mM dendrimer. Further studies of isothermal titration calorimetry (ITC) measurement show that the CAC of SDS in the presence of dendrimer remains invariant to the dendrimer concentration. Complexation reaction between SDS and dendrimer is highly exothermic in nature. A maximum heat release (ΔH∼ -6.6 kJ/mol of SDS binding) was observed at a SDS-to-dendrimer mole ratio of ∼3-5; where up to 3 to 5 SDS molecules were encapsulated by one dendrimer molecule to form dendrimer-SDS encapsulation complex. When negatively charged SDS was replaced with a positively charged surfactant dodecyl-trimethylammonium-bromide (DTAB), we found that the DTAB hardly interacted with positively charged dendrimer due to the charge-charge repulsions.