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 dep...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.展开更多
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...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.展开更多
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 aggr...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.展开更多
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...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.展开更多
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 an...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.展开更多
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 surfacta...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.展开更多
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^...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.展开更多
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 a...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.展开更多
Molecular dynamics (MD) simulation are used to study the properties of gemini surfactant of ethyl-α,ω-bis(dodecyldimethylammonium bromide) (C12C2C12) and dodecyl- trimethylammonium bromide (DTAB) at the air/water in...Molecular dynamics (MD) simulation are used to study the properties of gemini surfactant of ethyl-α,ω-bis(dodecyldimethylammonium bromide) (C12C2C12) and dodecyl- trimethylammonium bromide (DTAB) at the air/water interface, respectively. In the two systems, the surfactant concentrations are both 28 wt. %, and other conditions are also the same. After reaching the thermodynamic equilibrium, the concentration profiles, the radial distributions functions (RDF) and the mean squared displacement (MSD) are investigated. The results reveal that the surface activity of C12C2C12 surfactant is higher than DTAB surfactant.展开更多
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 ammoni...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.展开更多
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 flotatio...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.展开更多
A highly effective phase transfer of a quaternary ammonium gemini surfactant with ester groups（（diethylhexanedioate） diyl-a,v-bis（dimethyl dodecyl ammonium bromide） referred to as 12-10-12）was synthesized with h...A highly effective phase transfer of a quaternary ammonium gemini surfactant with ester groups（（diethylhexanedioate） diyl-a,v-bis（dimethyl dodecyl ammonium bromide） referred to as 12-10-12）was synthesized with high yield and characterized by infrared spectroscopy, elemental analysis and1 HNMR. Then, 12-10-12 was used as a phase transfer catalyst to study the catalytic effect on the reaction of anhydrous sodium acetate and 4-methylbenzyl chloride. The possible catalytic mechanism and the influence of surfactant concentration, temperature and type are also discussed. The experimental results showed that the catalysis efficiency was more active than the traditional, single-chained surfactant,tetrabutyl ammonium bromide. It also revealed that the reaction was first-order with respect to the concentration of 4-methylbenzyl chloride. The concentration of 4-methylbenzyl chloride grew linearly with the concentration of 12-10-12 and as the reaction temperature increased. The optimum reaction time was 7 h.展开更多
The rheological behavior of the aqueous solutions of mixed sulfate gemini surfactant with no spacer group, referred to as d-C12S, and dodecyltrimethylammonium bromide （C12TABr） at a total concentration of 100 mmol,L...The rheological behavior of the aqueous solutions of mixed sulfate gemini surfactant with no spacer group, referred to as d-C12S, and dodecyltrimethylammonium bromide （C12TABr） at a total concentration of 100 mmol,L-1 but different molar ratios of ClzTABr to d-C12S （a1） was investigated using steady rate and frequency sweep measurements. The wormlike micelles were formed over a narrow a1 range of 0.20-0.27. The viscoelastic solutions exhibited Maxwell fluid behavior. At the optimum molar ratio of 0.25, the zero-shear viscosity was as high as 600 paos and the length of the mixed wormlike micelle was about 0.45-0.85 pm. The present result provides an exam- ple to construct long wormlike micelles by anionic gemini surfactant.展开更多
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 w...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.展开更多
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 sodiu...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.展开更多
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, transm...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.展开更多
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 reporte...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.展开更多
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, ...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.展开更多
A new surfactant of Gemini-type,N,N'-((phthylbis(oxy))bis(ethane-2,1-diyl))bis(N,N-dimethyldodecan-1-aminium bromide)is prepped&confirmed.The dissolution suppression impact of the new compound on steel is perf...A new surfactant of Gemini-type,N,N'-((phthylbis(oxy))bis(ethane-2,1-diyl))bis(N,N-dimethyldodecan-1-aminium bromide)is prepped&confirmed.The dissolution suppression impact of the new compound on steel is performed in 1 mol·L^(-1)HCl environment by means of chemical and electrochemical methods.The prepared surfactant is an agreeable dissolution inhibitor for steel.The mitigation efficacy rises with the quantity of the compound.The surfactant belongs to inhibitors of mixed-type.The adsorption of the synthesized compound followed the Langmuir's model.The negative magnitudes of bothΔG_(ads)^(θ) andΔH^(adsθ)indicate that the adsorption process proceeds from its own accord and exothermic.The mechanism of adsorption is elucidated by scanning microscopy.It is established that the transfer resistance(R_(ct))value rose,where the value of the phase element(CPE)reduced with the amount of synthesized inhibitor.According to the experimental data arrived by surface tension measurements,the prepared compound is a powerful active agent at the air/water boundary.展开更多
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 t...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.展开更多
基金supported by the National Natural Science Foundation of China(U2001217,22261160370 and 21972006)Guangdong-Hong Kong-Macao Joint Innovation Foundation(2021A0505110003)+1 种基金Shenzhen Basic Research(JCYJ20220818101018038 and JCYJ20200109110628172)Guangdong Province Regional Joint Innovation Foundation(2020B1515120039)。
文摘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.
基金We are grateful for the financial support from the National Natural Science Foundation of China(29971001,20031010)the Naturai Science Foundation of Anhui Province(0045115)the Science Foundation for Excellent Young Teachers of Universities of Anhui Province(01080309).
文摘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.
基金Supported by the National Natural Science Foundation of China （No.20476025）, the Doctoral Research Foundation of the Ministry of Education of China （No.20050251004）, E-institute of Shanghai High Institution Grid （No.200303） and Shanghai Municipal Science and Technology Commission of China （No.05DJ14002）.
文摘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.
基金Supported by the National Natural Science Foundation of China （20706013, 20736002）, Program for Changjiang Scholars and Innovative Research Team in University （IRT0721）, the 111 Project （B08021） and National University of Singapore.
文摘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.
文摘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.
文摘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.
基金the Natural Science Foundation of Hubei Province, China (2000J023)
文摘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.
基金supported by the National Natural Science Foundation of China (No.21375145)
文摘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.
基金The authors gratefully acknowledge financial support from Key Technologies R&D Program Foundation of China(02BA312B07)the National Natural Science Foundation of China(No.20303011)Natural Science Foundation of Shandong Province(Y 2001 B08).
文摘Molecular dynamics (MD) simulation are used to study the properties of gemini surfactant of ethyl-α,ω-bis(dodecyldimethylammonium bromide) (C12C2C12) and dodecyl- trimethylammonium bromide (DTAB) at the air/water interface, respectively. In the two systems, the surfactant concentrations are both 28 wt. %, and other conditions are also the same. After reaching the thermodynamic equilibrium, the concentration profiles, the radial distributions functions (RDF) and the mean squared displacement (MSD) are investigated. The results reveal that the surface activity of C12C2C12 surfactant is higher than DTAB surfactant.
基金supported by National Natural Science Foundation of China(U21A200313)Key Program of Qingyuan Innovation Laboratory(00221003)‘111’program of Fuzhou University.
文摘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.
基金Project(2013AA064102)supported by the High-tech Research and Development Program of ChinaProject(51004114)supported by the National Natural Science Foundation of China+1 种基金Project(2007B52)supported by the Foundation for the Author of National Excellent Doctoral Dissertation of ChinaProject(NCEP-08-0568)supported by the Program for New Century Excellent Talents in Chinese University
文摘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.
基金supported by the Talent Foundation of Anhui Science and Technology University (No. ZRC2014401)
文摘A highly effective phase transfer of a quaternary ammonium gemini surfactant with ester groups（（diethylhexanedioate） diyl-a,v-bis（dimethyl dodecyl ammonium bromide） referred to as 12-10-12）was synthesized with high yield and characterized by infrared spectroscopy, elemental analysis and1 HNMR. Then, 12-10-12 was used as a phase transfer catalyst to study the catalytic effect on the reaction of anhydrous sodium acetate and 4-methylbenzyl chloride. The possible catalytic mechanism and the influence of surfactant concentration, temperature and type are also discussed. The experimental results showed that the catalysis efficiency was more active than the traditional, single-chained surfactant,tetrabutyl ammonium bromide. It also revealed that the reaction was first-order with respect to the concentration of 4-methylbenzyl chloride. The concentration of 4-methylbenzyl chloride grew linearly with the concentration of 12-10-12 and as the reaction temperature increased. The optimum reaction time was 7 h.
基金Project supported by the Fundamental Research Funds for the Central Universities （No. JUSRP111A06）, the National Natural Science Foundation of China （Nos. 20673021, 20873024 and 21073081）, the Professional Foundation of Fuzhou University （No. XRC-0639）, and the Fujian Provincial Natural Science Foundation of China （No. 2010J01038）.
文摘The rheological behavior of the aqueous solutions of mixed sulfate gemini surfactant with no spacer group, referred to as d-C12S, and dodecyltrimethylammonium bromide （C12TABr） at a total concentration of 100 mmol,L-1 but different molar ratios of ClzTABr to d-C12S （a1） was investigated using steady rate and frequency sweep measurements. The wormlike micelles were formed over a narrow a1 range of 0.20-0.27. The viscoelastic solutions exhibited Maxwell fluid behavior. At the optimum molar ratio of 0.25, the zero-shear viscosity was as high as 600 paos and the length of the mixed wormlike micelle was about 0.45-0.85 pm. The present result provides an exam- ple to construct long wormlike micelles by anionic gemini surfactant.
基金financial support by the Key Program for Scientific and Technological Innovations of Higher Education Institutes in Guangdong Province(No.CXZD1022)
文摘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.
基金the National Natural Science Foundation of China (No. 20025618, No. 20236010) Shanghai Municipal Education Commission of China.
文摘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.
基金supported by the National Natural Science Foundation of China (20932004)the Prospective Basic Research Subject of China Petroleum (P07009)
文摘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.
文摘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.
文摘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.
文摘A new surfactant of Gemini-type,N,N'-((phthylbis(oxy))bis(ethane-2,1-diyl))bis(N,N-dimethyldodecan-1-aminium bromide)is prepped&confirmed.The dissolution suppression impact of the new compound on steel is performed in 1 mol·L^(-1)HCl environment by means of chemical and electrochemical methods.The prepared surfactant is an agreeable dissolution inhibitor for steel.The mitigation efficacy rises with the quantity of the compound.The surfactant belongs to inhibitors of mixed-type.The adsorption of the synthesized compound followed the Langmuir's model.The negative magnitudes of bothΔG_(ads)^(θ) andΔH^(adsθ)indicate that the adsorption process proceeds from its own accord and exothermic.The mechanism of adsorption is elucidated by scanning microscopy.It is established that the transfer resistance(R_(ct))value rose,where the value of the phase element(CPE)reduced with the amount of synthesized inhibitor.According to the experimental data arrived by surface tension measurements,the prepared compound is a powerful active agent at the air/water boundary.
文摘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.
