Micellar Exchange Kinetics of Quaternary Ammonium Type Gemini Surfactants Monitored by Nuclear Magnetic Resonance

The dynamic NMR （DNMR） method was used to detect kinetic parameters of the molecular exchange process between monomers in bulk solution and those in the micelle for Gemini surfactants, 12-s-12 and 14-s-14 （s 2, 3 and 4）. The escape rate constant, k^- , was derived based on the simplified equations of DNMR theory, and the apparent activation energy of escape, Ea^- , was obtained based on the Arrhenius equation through temperature variation experiments. Results show that the orders of magnitude of k^- for 14-s-14 and 12-s-12 are respectively 10 and 103 s-1, Ea^- of 14-s-14 and 12-s-12 are respectively 54.04-73.64 and 33.42-47.09 kJ/rnol. Furthermore, k increases and Ea^- decreases with the spacer length growing. In combination with the rnicro-polarity measurements, it was revealed that molecules of 14-s-14 and 12-s-12 have to experience conformation changes when escaping from the rnicelles. The two-step molecular exchange mechanism for Gemini surfactants was therefore supported.

Synthesis and Surface Activity of Novel Triazole-based Cationic Gemini Surfactants

The synthesis and surfactant activities of two new cationic gemini surfactants containing triazole compound as spacer were described. Their critical micelle concentrations (CMC), which are 1.8×10-4 mol/L and 3.9×10-4 mol/L respectively, are much lower than that of conventional surfactant cetyltrimethyl ammonium chloride (CTAC). In addition, compared with some gemini surfactants containing phenylene, xylylene and stilbenyl as spacer, this new kind of surfactants has good solubility in water at room temperature because of containing more hydrophilic groups or atoms in molecules.

Biphasic Catalytic Hydroformylation of 1-Dodecene in Micellar System with Cationic Gemini Surfactants

The promotion effect of cationic gemini surfactants for the hydroformylation of 1-dodecene in the organic/aqueous biphasic catalytic system is reported. The hydroformylation reaction in the presence of gemini surfactant occurred with higher turnover frequency and higher selectivity for linear aldehyde than using conventional monomeric surfactant CTAB.

Synthesis and Surface Activity of Biquaternary Ammonium Salt Gemini Surfactants with Ester Bond

The synthesis and surface activity of gemini surfactants with ester bond as spacer are described. Their critical micelle concentrations （CMC） are much lower than that of conventional surfactants, i.e., 1.62×10^-5, 1.38×10^-5, 1.28×10^-5 mol·L^-1 for gemini Ⅰ, Ⅱ and Ⅲ respectively. Surface tension at the CMC of gemini Ⅰ, Ⅱ and Ⅲ were 36.4, 38.5, 41.2 mN · m^-1. The physico-chemical properties such as Krafft points, foaming abilities and emulsifying power were also investigated. It is found that the title compounds have low Krafft points and show good solubility in water. The gemini surfactants synthesized also exhibit good foaming properties and excellent emulsifying power toward toluene. The foaming abilities and emulsifying power increase with the increase in carbon number of hydrophobic chain, and this might be caused by the sheer viscosity of different gemini surfactant solution.

Surface activity and cleaning performance of rosin-based quaternary ammonium salt type asymmetric Gemini surfactants

Rosin,a renewable and abundant resource,has been extensively processed and chemically modified to endow it with special properties,especially in the surfactant industry.In this study,four rosin-based quaternary ammonium asymmetric gemini surfactants(RGS-2-n)with different alkyl chain lengths(n=12,14,16,18)were synthesized using a simple two-step method based on dehydroabietylamine as the raw material.The feasibility of these surfactants for cleaning purposes was comprehensively evaluated,suggesting that the surfactants own high surface activity and good cleaning performance.Furthermore,by successfully introducing the amine group of dehydroabietylamine into the hydrophilic group of the surfactants,we avoided its potential harm to the environment and water pollution.Density functional theory proves rosin-based gemini surfactants with asymmetric structure can further improve cleaning efficiency.Overall,our findings suggests that RGS-2-n surfactants are promising and sustainable candidates for cleaning electric plates,and provide new opportunities for rosin application in the electric industry.

Comparative studies on flotation of aluminosilicate minerals with Gemini cationic surfactants BDDA and EDDA

Gemini quaternary ammonium salt surfactants, butane-a, co-bis（dimethyl dodeculammonium bromide） （BDDA） ethane-a, fl-bis（dimethyl dodeculammonium bromide） （EDDA） were adopted to comparatively study the flotation behaviors of kaolinite, pyrophyllite and illite. It was found that three silicate minerals all exhibited good floatability with Gemini cationic surfactants as collectors over a wide pH range, while BDDA showed a stronger collecting power than EDDA. FTIR spectra and zeta potential analysis indicated that the mechanism of adsorption of Gemini collector molecules on three silicate minerals surfaces was almost identical for the electronic attraction and hydrogen bonds effect. The theoretically obtained results of density functional theory （DFT） at B3LYP/6-31G （d） level demonstrated the stronger collecting power of BDDA presented in the floatation test and zeta potential measurement.

Synthesis and properties of novel cationic gemini surfactants with adamantane spacer

Novel quaternary ammonium cationic gemini surfactants, with two hydrocarbon chains and an adamantane core, were designed and synthesized by three-step reactions from adamantane. The structure of obtained surfactants were confirmed by 1H NMR, FTIR and elements analysis and the surface properties of these surfactants were also studied by surface tension measurements. These target surfactants exhibit much lower critical micelle concentrations （CMC） and higher efficiency in lowering the surface tension of water than typical surfactants.

ESR Studies on the Micellization Behaviors of a Series of Novel Asymmetric Gemini Surfactants

The synthesis of a new series of asymmetric cationic gemini surfactant and the investigation of their micellization behaviors by electronic spin resonance (ESR) as well as the surface tension measurements were reported. 4 Oxo 2,2,6,6 te^tra^me^thyl^pi^pe^ri^dine N oxyl (4 oxo TEMPO) is used as the spin probe. The surfactants studied have the general formula [C n H 2 n +1 N +(CH 3) 2C 6H 12 N +(CH 3) 2C m H 2 m +1 ]Br 2 -, referred to as dimeric n 6 m surfactants, in which n and m are the numbers of carbon atoms in the asymmetric side alkyl chains. From the experimental data, rotational correlation time τ c, surface tension and critical micelle concentration (cmc) values, the physical properties of these new surfactants have preliminarily been evaluated. It is shown that this new series of asymmetric gemini surfactants has interesting micellization behaviors, and they are very different in aggregating tendency from their asymmetric analogues.

Novel Piperazine-based Gemini and Bola Surfactants

A series of piperazine-based Gemini and Bola surfactants were synthesized. Gemini 1 and 5 have well surface activities. Their critical micelle concentrations （cmc） is 6.47×10^-4 mol/L and 1.17×10^-3mol/L, respectively. Bola surfactants 2 and compound 3, possessing better water solubility, have lower surface activities. Calculation, carried out by MM2 energy minimization, showed that compound with more hydrophobic chains in a spacer of limited length is difficult to be synthesized.

Synthesis and Properties of Gemini Cationic Surfactants with Amide Spacers

Four gemini cationic surfactants {N,N′-di[2-(lauryldimethylamino)acetyl]polymethylenediamine dichloride, LAA-s-LAA, s=2,3,4,6} were synthesized by using four bis(α-chloroacetamide)s and N,N-dimethyllaurylamine, respectively. The molecular structures were characterized by means of IR, ~ 1H NMR, \{~ ~13 C NMR\} and MS, and the behavior of their aqueous solutions was studied. The critical micell concentrations(CMC) of LAA-s-LAA were one order of magnitude lower than that of dodecyltrimethyl ammonium chloride(DTAC). With the change of the length of spacer chain(s), their CMC values change, and CMC reaches the top value at s=4.

Phase Separation and Microstructure of Mixed Surfactants Solution Containing Cationic Geminis and Traditional Anionic Surfactant

The properties of aqueous two-phase system (ATPS) of mixed solution containing gemini cationic surfactant trimethylene-1,3-bis(dodecyldimethyl ammonium) bromide (12-3-12, 2Br-) and traditional anionic surfactant sodium dodecyl sulfate (SDS) with or without added salt have been studied. An ATPS is formed in a narrow region of the ternary phase diagram different from that of traditional aqueous cationic-anionic surfactant systems. In ATPS region, the lowest total concentration of surfactants varies with the mixing ratio of geminis to SDS. Photographs obtained from freeze-etching, negative-staining and transmission electron microscopy show that the microstructures of two phases are different from each other. Micelles and vesicles can coexist in a single phase. The addition of salts can change the phase diagram of ATPS. Furthermore, the added salts promote the aggregation of rod-like micelles to form coarse network structure that increase the viscosity of solutions. The negative ions of the added salts are the determining factor.

Supramolecular vesicles of cationic gemini surfactants modulated by p-sulfonatocalix[4]arene

Supramolecular binary vesicles were constructed by host-guest complex formation between p-sulfonatocalix[4]arene and three cationic gemini surfactants, which were identified by UV-vis, dynamic laser scattering, transmission electron microscopy, scanning electron microscopy, atomic force microscopy, and surface tension experiments. The critical aggregation concentration of gemini surfactants decreased pronouncedly by a factor of ca. 1000 owing to the complexation of p-sulfonato-calix[4]arene.

Gemini Surfactants Templated Mesoporous Silica Microparticles： from Solid to Hollow Mesoporous Spheres

We synthesized a series of mesoporous silica microparticles （MSs） using cationic gemini surfactants C14.2-n （n=2, 6, 10, 14） as templates. The porous structures and pore size of these MSs can be tuned by varying the length of alkyl chain in gemini surfaetant templates. These MSs showed effective doxorubicin （DOX） loading and a pH-responsive drug release characteristics. These results indicate that the MSs, especially the hollow mesoporous silica nanoparticles, have great potential for biomedical applications.

Long-Chain Gemini Surfactant-Assisted Blade Coating Enables Large-Area Carbon-Based Perovskite Solar Modules with Record Performance

Carbon-based perovskite solar cells show great potential owing to their low-cost production and superior stability in ambient air.However,scaling up to high-efficiency carbon-based solar modules hinges on reliable deposition of uniform defect-free perovskite films over large areas,which is an unsettled but urgent issue.In this work,a long-chain gemini surfactant is introduced into perovskite precursor ink to enforce self-assembly into a network structure,considerably enhancing the coverage and smoothness of the perovskite films.The long gemini surfactant plays a distinctively synergistic role in perovskite film construction,crystallization kinetics modulation and defect passivation,leading to a certified record power conversion efficiency of 15.46%with Voc of 1.13 V and Jsc of 22.92 mA cm^(-2)for this type of modules.Importantly,all of the functional layers of the module are printed through a simple and high-speed(300 cm min^(-1))blade coating strategy in ambient atmosphere.These results mark a significant step toward the commercialization of all-printable carbon-based perovskite solar modules.

Interaction of antipsychotic drug with novel surfactants: Micellization and binding studies

The interaction of cationic gemini surfactants(alkanediyl-α,ω-bis(alkyl dimethylammonium bromide)) with an antipsychotic drug(chlorpromazine hydrochloride(CPZ)) has been investigated. Various micellar and interfacial parameters have been deliberated by surface tension measurement to report the nature of interactions between drug and novel surfactant mixtures. The behavior of mixed systems, their compositions and activities of components have been analyzed in the light of Rubingh's theory. The results indicate synergism in the binary mixtures.The binding study between CPZ and surfactants has been done by spectroscopic techniques such as UV–visible and fluorescence. The results are discussed in the light of the use of gemini surfactants as promising drug delivery agents for phenothiazine drugs, and hence, improve their bioavailability.

Molecular Dynamics Simulation for the Effect of Chain Length of Spacer and Tail of Cationic Gemini Surfactant on the Complex with Anionic Polyelectrolyte

Interaction of anionic polyelectrolyte with cationic gemini surfactant has been investigated by coarse-grained molecular dynamics simulation.Polyelectrolyte facilitates the oppositely charged ionic surfactants to aggregate by suppressing the electrostatic repulsion between ionic head groups leading to the formation of micellar complex.With addition of surfactant,the conformation of polyion chain changes from stretched to random coiled to spherical,and at the same time more free micelles are formed by surfactants in mixtures.Increasing the length of spacer or tail chain in gemini surfactant will weaken its interaction with polyelectrolyte and simultaneously strengthen its tendency to self-assemble.The simulation results are consistent with experimental observations and reveal that the electrostatic interaction plays an important role in the interaction of polyelectrolyte with gemini sur- factant.

Flotation techniques for separation of diaspore from bauxite using Gemini collector and starch depressant

The floatability of diaspore and three kinds of silicate minerals,including kaolinite,illite and pyrophyllite,by a cationic Gemini surfactant as collector and starch as depressant was investigated as function of reagents concentration and pulp pH.Further studies of artificially mixed minerals and bauxite ore were also detailedly conducted.At last,the pre-desliming reverse flotation separation process was adopted.It can be concluded that the combinational use of a Gemini cationic collector and the starch depressant is effective.The concentrates with Al2O3 to SiO2 mass ratio of 9.66 and the recovery of Al2O3 of 71.73% are obtained from natural bauxite ore(A/S=5.70) at pH value of around 10.

Flotation performance of a novel Gemini collector for kaolinite at low temperature

How to sustainably produce bauxite by effective reverse froth flotation of kaolinite at low temperature is an urgent problem to be solved in the field of mineral processing.In this work,a novel amino-based Gemini surfactant butadiyl-1,4-bis(dimethyl dodecylammonium bromide)(BBDB) was prepared and first utilized as a novel collector for kaolinite flotation.Its flotation performance for kaolinite was compared with that of the common monomolecular surfactant 1-dodecylamine(DDA) by micro-flotation tests.The tests results indicated that 95% kaolinite recovery was obtained using 2.0×10^(-4) mol/L BBDB at 25℃ which was half of the dosage when DDA obtained the maximum kaolinite recovery of81%.At extremely low temperature(0℃),3.0×10^(-4) mol/L BBDB could still collect 91% kaolinite,while DDA showed a frustrating ability.The contact angle tests indicated that BBDB could still significantly improve the hydrophobicity of the kaolinite surface(contact angle 71.7°) than DDA(contact angle only25.8°) at 0℃.The Krafft point comparison tests indicated that BBDB had a much lower Krafft point(below0℃) than DDA.Fourier transform infrared spectroscopy(FTIR)-spectrum analysis and zeta potential measurements showed that BBDB was physically adsorbed on the surface of kaolinite through electrostatic interaction.

Interaction of DNA with Cationic Gemini Surfactant Trimethylene-1, 3-bis （dodecyldimethyl-ammonium bromide） and Anionic Surfactant SDS Mixed System

The interaction of DNA with cationic gemini suffactant trimethylene-1,3-bis （dodecyl dimethyl-ammonium bromide） （12-3-12） and anionic surfactant sodium dodecyl sulfate （SDS） mixed system has been investigated by measuring the fluorescence, zeta potential, UV-Vis spectrum, and circular dichroism. In the absence of SDS, owing to the electrostatic and hydrophobic interactions, 12-3-12 forms micelle-like structure on the DNA chain before the micellization in bulk phase. For the mixed system of 12-3-12 and SDS, the negative charges on SDS can compete against DNA to bind with cationic 12-3-12 because of the stronger interaction between oppositely charged surfactants, and thus, the catanionic mixed micelles are formed before the formation of DNA/12-3-12 complexes. There-after, the positive charges on the mixed micelles bind with DNA, and thus, the change of the zeta potential from negative to positive is distinctly different from the system without SDS. Meanwhile, the existence of SDS postpones the exclusion of ethidium bromide （EB） from DNA/EB complexes. The conformation of DNA undergoes a change from native B-form to chiral ψ-phase as binding with 12-3-12 process. Upon adding SDS to the DNA/12-3-12 complex solution, however, DNA is released to the bulk and the ψ-phase returns to B-form again.

Interaction in Binary Mixtures of Gemini Surfactant G12-6-12 and CTAB by NMR

The interaction between N, N′-bis（dimethyldodecyl）-1,6-hexanediammoniumdibromide （G12-6-12） and cetyltrimethylammonium bromide （CTAB） in D20 aqueous medium has been investigated by NMR at 298 K. The G12-6-12 and CTAB are about 0.773 and measured critical micelle concentration （cmc） of 0.668 mmol/L, respectively. The cmc^＊ （cmc of mixture） values are less than CMC^＊ （cmc of ideally mixed solution） in the mixed system, and the interaction parameter βM〈0 at different molar fractions α of G12-6-12 in the mixed systems, but just when α≤0.3, cmc^＊ values are much smaller than CMC^＊, and βM satisfies the relation of ｜βM｜〉｜ln（cmc1/cmc2）｜ （cmcl： cmc of pure G12-6-12 and cmc2： cmc Of pure CTAB）. The results indicate that there exists synergism between G12-6-12 and CTAB, and they can form mixed micelles, which is further proven by 2D NOESY and self-diffusion coefficient D experiments. There are intermolecular cross peaks between G12-6-12 and CTAB in 2D NOESY, and the radius of micelles in mixed solution is bigger than that in G12-6-12 pure solution in D experiments, indicating there are mixed micelles. However, when α〉0.3, we find that cmc^＊≈CMC^＊, βM≈0, obviously, the two surfactants are almost ideal mixing fitting the pseudo-phase separation model and regular solution theory.