Surfactant mediated control of pore size and morphology for molecularly ordered ethylene-bridged periodic mesoporous organosilica

A series of ethylene-containing mesoporous organosilica materials were fabricated via surfactant-mediated assembly of 1,2-bis(triethoxysilyl)ethylene (BTEE) organosilica precursor using alkyltrimethylammonium bromide (CnTAB) surfactants with different alkyl chain length (n=12, 14, 16, 18) as supramolecular templates. The presence of molecularly ordered ethylene groups in the resulting periodic mesoporous organosilica (PMO) materials was confirmed by XRD data along with 29Si and 13C MAS NMR analysis. Additional characterization techniques, namely nitrogen sorption, TEM, and TGA, confirmed the structural ordering and thermal stability of the molecularly ordered ethylene-bridged PMOs. The PMOs exhibit molecular-scale ordering (with a periodicity of 5.6 A) within the organosilica framework and tunable pore size, which depending on the alkyl chain length of the surfactant templates, varied in the range 23-41 A. Furthermore, depending on the alkyl chain length of the templates, the particle morphology of the PMOs gradually changed from monodisperse spheres (for C12TAB) to rod or cakelike particles (for C14TAB) and elongated ropelike particles for longer chain surfactants. Variations in the surfactant chain length therefore allowed control of both the pore size and particle morphology without compromising molecular-scale or structural ordering. The reactivity of ethylene groups was probed by bromination, which demonstrated the potential for further functionalization of the PMOs.     

N-烷基化聚对苯二甲酰对苯二胺梳状高分子中烷基侧链对刚性主链堆积行为的影响

基于聚对苯二甲酰对苯二胺(PPTA), 采用N-烷基化方法制备了系列PPTACns(烷基侧链碳原子数n=8, 10, 12, 14, 16, 18)刚性主链梳状高分子, 利用DSC, XRD和FTIR等方法研究了其主链堆积行为、 分子链构象及热性能等与烷基侧链长度及结晶特性之间的关系. XRD和DSC结果表明, 当烷基侧链碳原子数达到14时, 烷基侧链发生结晶. XRD结果显示, PPTACns具有层状结构, 烷基侧链长度对主链层间距影响显著. FTIR研究发现, 烷基侧链的聚集状态对PPTACns分子链的构象产生较大影响, 伴随着烷基侧链结晶的熔融, PPTACns的分子链构象发生显著改变. 烷基侧链处于熔融状态的PPTACns的ν_C=O和γ_C-H谱带峰位与烷基侧链不结晶的PPTACn接近.     

Mesomorphous Structure and Electrochemical Behavior of Polyelectrolyte-Ferrocenyl Surfactant Complexes

Redox-active polyelectrolyte-surfactant complexes (PSC) were prepared via the ionic self-assembly of sodium polyacrylate (PAAS) and ferrocenyl surfactant, n-alkyl (ferrocenylmethyl)ammonium bromide (Fcn, n = 8, 12, 16, where n is the carbon number of the alkyl chain), in solution. The obtained PAAS-Fcn complex exhibited crystalline and lamellar mesomorphous structure. Moreover, the ferrocenyl moieties formed H-aggregation in the solid complex as known from the blue shift in the ultraviolet-visible spectrum. Cyclic voltammogram (CV) measurements indicated that the reversibility of the electrode process became worse when the surfactant tail length increases because of the more ordered packing in the complex film formed by longer surfactant tails. The present results demonstrate that the electrochemical activity of the redox-active polyacrylate-ferrocenyl surfactant complex can be easily tuned by changing the surfactant tail length. Our work provides a simple and facile approach to the preparation of redox-active polymers with ordered mesomorphous structure by the ionic self-assembly.     

Characterization of the aggregates of N-alkyl-N-methylpyrrolidinium bromide surfactants in aqueous solution

We have characterized a new class of surfactant molecules using fluorescence spectroscopic and light-scattering techniques. Our results suggest that this homologous series of N-alkyl-N-methlypyrrolidinium bromide (CnMPB) surfactants with n = 10, 12, 14, 16, and 18 represents a bridge between the well-characterized alkyltrimethylammonium bromide (CnTAB) and dialkyldimethylammonium bromide (di-CnDAB) surfactant series. For the smaller members of the CnMPB series with n = 10, 12, and 14, our results are consistent with the formation of spherical micelles as the surfactant concentration is increased. With increasing alkyl chain length, we observe that the critical micelle concentration decreases and the aggregation number increases, typical of single-tail surfactants. For C16MPB, the formation of micelles at dilute concentrations (0.10 mM) is likely, followed by the coexistence of micelles and small unilamellar vesicles at higher concentrations up to 0.82 mM where only vesicles are present. For C18MPB, our data are consistent with the formation of vesicles only. We demonstrate in this study that the combination of spectroscopic and light-scattering methods is a powerful approach to reveal aspects of aggregate structure and morphology in aqueous CnMPB surfactant systems. In particular, the sensitivity of the fluorescence probe prodan to the polarity of its microenvironment enables the rich complexity of surfactant aggregates exhibited by this series of amphiphilic molecules to be detected.     

Preparation and Characteration of UV-cured EA/MMT Nanocomposites Via In-Situ Polymerization

A long-chain surfactant, enzoylbenzyl-N,N-dimethyl-N-octadecylammonium bromide (BDOB) with a benzophenone group, was synthesized to modify the montmorillonites (MMT) for the preparation of nanocomposites via photo-induced polymerization. The BDOB-modified MMT was characterized by the fourier transform infrared spectrometer (FTIR), thermal gravimetric analyzer (TGA) and X-ray diffraction (XRD), and the results of XRD indicated that the intercalated structures of BDOB-modified MMT was obtained. The conversion of the bisphenol A epoxy diacrylate (EA) was quantified by the FTIR, and the results indicated that conversion increased with an increase in the amount of BDOB-modified MMT. The morphologies of the UV-cured EA/MMT nanocomposites prepared from this organically modified MMT were studied by means of XRD and TEM, and the results showed that all the samples contained an intercalated structure with partial exfoliated structure. The results of TGA and mechanical properties also indicated that the thermal and mechanical properties of UV-cured nanocomposites were significantly enhanced due to the presence of the long chain surfactant organically modified MMT.     

Study of complexes between lysozyme and sodium alkyl sulfates in the solid state

Complexes between lysozyme and sodium alkyl sulfates (decyl, dodecyl, tetradecyl and hexadecyl) in the solid state were prepared by mixing aqueous solutions of lysozyme and of the surfactant, separating the precipitated complex and purifying it. The stoichiometry of the complexes was investigated by elemental analysis and was found to correspond to about 8ǃ alkyl sulfate ions per lysozyme. Low- and wide-angle X-ray scattering were used to investigate the structure of the complexes. The scattering curves showed one fairly large scattering maximum, revealing a low state of organization of the complexes. The characteristic length characterizing the complexes was calculated from the value of the wave vector corresponding to the maximum of the scattered intensity. This length increased by about 0.233 nm per additional methylene group in the surfactant alkyl chain. A model where spherical aggregates of alkyl sulfate ions are arranged in a disordered simple cubic structure, dispersed in a matrix of lysozyme, provides a possible explanation of the results.     

长链烷基季铵盐插层氧化石墨的结构变化

基于改进的Hummers法制备氧化石墨(GO),并以长链烷基季铵盐(C_nTAB)对其进行插层处理;通过改变C_nTAB的链长、浓度,得到系列C_nTAB/GO插层复合物。采用XRD和元素分析对产物的最大底面间距及C_nTAB插入量进行表征。结果表明,随着C_nTAB链长的增长、C_nTAB浓度的增大,C_nTAB/GO插层复合物的最大底面间距逐渐增大。C_nTAB通过离子键作用和疏水键作用插入到GO层间,在GO片层上的吸附规律符合修正型(Modified)Langmuir模型,即C_nTAB以单分子层吸附在GO片层上。根据C_nTAB/GO插层复合物最大底面间距及C_nTAB插入量的变化规律分析,得出C_nTAB在GO层间的排布模式有单层平躺模式、类双层平躺模式、单层倾斜模式和单层直立模式。     

Structure of DNA-cationic surfactant complexes at hydrophobically modified and hydrophilic silica surfaces as revealed by neutron reflectometry

In this article, we discuss the structure and composition of mixed DNA-cationic surfactant adsorption layers on both hydrophobic and hydrophilic solid surfaces. We have focused on the effects of the bulk concentrations, the surfactant chain length, and the type of solid surface on the interfacial layer structure (the location, coverage, and conformation of the DNA and surfactant molecules). Neutron reflectometry is the technique of choice for revealing the surface layer structure by means of selective deuteration. We start by studying the interfacial complexation of DNA with dodecyltrimethylammonium bromide (DTAB) and hexadecyltrimethylammonium bromide (CTAB) on hydrophobic surfaces, where we show that DNA molecules are located on top of a self-assembled surfactant monolayer, with the thickness of the DNA layer and the surfactant-DNA ratio determined by the surface coverage of the underlying cationic layer. The surface coverages of surfactant and DNA are determined by the bulk concentration of the surfactant relative to its critical micelle concentration (cmc). The structure of the interfacial layer is not affected by the choice of cationic surfactant studied. However, to obtain similar interfacial structures, a higher concentration in relation to its cmc is required for the more soluble DTAB surfactant with a shorter alkyl chain than for CTAB. Our results suggest that the DNA molecules will spontaneously form a relatively dense, thin layer on top of a surfactant monolayer (hydrophobic surface) or a layer of admicelles (hydrophilic surface) as long as the surface concentration of surfactant is great enough to ensure a high interfacial charge density. These findings have implications for bioanalytical and nanotechnology applications, which require the deposition of DNA layers with well-controlled structure and composition.     

Removal of solvent-based ink from printed surface of HDPE bottles by alkyltrimethylammonium bromides: effects of surfactant concentration and alkyl chain length

Three alkyltrimethylammonium bromides (i.e., dodecyl-, tetradecyl-, and hexadecyltrimethylammonium bromide or DTAB, TTAB, and CTAB, respectively) were used to remove a blue solvent-based ink from a printed surface of high-density polyethylene bottles. Either an increase in the alkyl chain length or the surfactant concentration was found to increase the deinking efficiency. Complete deinking was achieved at concentrations about 3, 8, and 24 times of the critical micelle concentration (CMC) of CTAB, TTAB, and DTAB, respectively. For CTAB, ink removal started at a concentration close to or less than its CMC and increased appreciably at concentrations greater than its CMC, while for TTAB and DTAB, significant deinking was only achieved at concentrations much greater than their CMCs. Corresponding to the deinking efficiency of CTAB in the CMC region, the zeta potential of ink particles was found to increase with increasing alkyl chain length and concentration of the surfactants, which later leveled off at some higher concentrations. Wettability of the surfactants on an ink surface increased with increasing alkyl chain length and concentration of the surfactants. Lastly, solubilization of ink binder in the surfactant micelles was found to increase with increasing alkyl chain length and surfactant concentration. We conclude that adsorption of surfactant on the ink pigment is crucial to deinking due to modification of wettability, zeta potential, pigment/water interfacial tension, and dispersion stability. Solubilization of binder (epoxy) into micelles is necessary for good deinking because the dissolution of the binder is required before the pigment particles can be released from the polymer surface.     

Interaction of cationic surfactants with carboxymethylcellulose in aqueous media

We have examined the polymer-surfactant interaction in mixed solutions of the cationic surfactants, i.e., dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, tetradecyltriphenylphosphonium bromide, and tetradecylpyridinium bromide and a semiflexible anionic polyelectrolyte carboxymethylcellulose in water and aqueous salt solutions by various techniques: tensiometry, viscosimetry or ion-selective electrode method, and dynamic light scattering. We have investigated the effect of varying surfactant chain length, head group size, counterion, and ionic strength on the critical aggregation concentration (CAC) of mixed polymer surfactant systems and the collapse of the polymer molecule under different solution conditions. The CAC decreases with increasing alkyl chain length. Above a certain surfactant concentration, mixed aggregates start growing until their macroscopic phase separation. The growth is more rapid with greater surfactant tail length and with increasing head group size. This is attributed in both cases to the increasing hydrophobic interaction between polymer and surfactant. Among surfactants with monovalent halide counterions, iodide induces the strongest binding, reflected by the onset of growth of the mixed aggregates at low surfactant concentration. This is perhaps related to the decreasing hydration of the counterion from chloride to iodide. The surfactant concentration at which the viscosity of the solution starts to decrease sharply is smaller than the CAC, and probably reflects polymer chain shrinkage due to noncooperative binding.     

Structure and composition of cationic-nonionic surfactant mixed adsorbed layers on mica

The composition and morphology of mixed adsorbed layers comprising one of several poly(oxyethylene) alkyl ether nonionic surfactants, C(i)E(j), and two cationic surfactants-dodecyltrimethylammonium bromide (DTAB) and tetradecyltriethylammonium bromide (TTeAB)-at the mica/solution interface have been studied using depletion adsorption and atomic force microscopy. The nonionic surfactants do not themselves adsorb onto mica, but can coadsorb with a cationic surfactant. The extent of their hydrophobic association with the adsorbed cationic surfactant depends on alkyl chain length, while the adsorbed layer morphologies are sensitive to the number of ethoxy groups. Nonionic surfactants with headgroups containing less than eight ethylene oxide units decrease the adsorbed aggregate curvature, gradually transforming globular TTeAB or cylindrical DTAB adsorbed aggregates into a rod, mesh, or bilayer structure. Those with larger headgroups favor globular aggregates. The mechanism by which the nonionic surfactant modifies the adsorbed morphology is the formation of defects in the form of cylinder end-caps or branch-points, leading to adsorbed layer compositions that differ from ideal mixing predictions. All mixed adsorbed films become saturated with the nonionic component when the capacity of the aqueous side of the adsorbed layer is reached.     

Preparation of Tube‐Like ZrO2/NaCl by Microemulsion Method

On the basis of w/o microemulsion and surfactant template‐assembly technology, tube‐like ZrO₂/NaCl was prepared using sodium bicarbonate as precipitant. The w/o microemulsion consisted of a nonionic surfactant OP emulsifier, cosurfactant pentanol and oil hexamethylene alkyl. The morphology, structure, and optical properties of the tube‐like ZrO₂/NaCl have been studied by SEM, XRD, FTIR, UV‐vis, and PL techniques.     

Preparation and characterization of zwitterionic surfactant-modified montmorillonites

A series of zwitterionic surfactant-modified montmorillonites (ZSMMs) were synthesized using montmorillonite and three zwitterionic surfactants with different alkyl chain lengths at different concentrations [0.2-4.0 cation exchange capacity (CEC)]. These ZSMMs were characterized by X-ray diffraction (XRD), thermo-gravimetric analysis and differential thermo-gravimetric (TG/DTG) analyses. The zwitterionic surfactant could be intercalated into the interlayer spaces of montmorillonites and causing interlayer space-swelling. From XRD measurements, the amount of the surfactants loaded and the basal spacing increased with surfactant concentration and alkyl chain length. One endothermic DTG peak occurred at ~390 °C, which was assigned to the decomposition of the zwitterionic surfactant on the organo-montmorillonites from 0.2 to 0.6 CEC. When the surfactant loading was increased, a new endothermic peak appeared at ~340 °C. From the microstructures of these ZSMMs, the mechanism of zwitterionic surfactant adsorption was proposed. At relatively low loadings of the zwitterionic surfactant, most of surfactants enter the spacing by an ion-exchange mechanism and are adsorbed onto the interlayer cation sites. When the concentration of the zwitterionic surfactant exceeds the CEC of montmorillonite, the surfactant molecules then adhere to the surface-adsorbed surfactant. Some surfactants enter the interlayers, whereas the others are attached to the clay surface. When the concentration of surfactant increases further beyond 2.0 CEC, the surfactants may occupy the inter-particle space within the house-of-cards aggregate structure.     

聚紫精-脂肪酸盐表面活性剂复合物的组装合成及相行为研究

通过Menshutkin反应合成聚(对亚二甲苯基-4,4'-联吡啶二溴)(PXV)半刚性链聚紫精,采用等量混合法将聚紫精与系列不同碳链长度的阴离子表面活性剂脂肪酸钠Cn-1COONa(n=10,12,14,16,18)组装制备聚电解质-表面活性剂(PXV-Cn)复合物,运用DSC,TGA,XRD,FTIR等表征手段初步考察复合物的超分子结构及相行为.基于FTIR谱学分析特征、小角与广角变温XRD数据以及DSC热分析焓变的定量计算结果,表明半刚性主链聚紫精和脂肪酸盐极性头基组成的极性层与侧链烷烃非极性层交替排列形成层状超分子结构,其中烷烃链靠近极性端约8个亚甲基处于无定型态,其余碳链则形成结晶相.最短的PXV-C10形成少量规整度较低的三斜晶βT,n≥16以上的长碳链复合物则以六方相αH为主,其它中等长度侧链脂肪酸盐复合物则为多种结晶形式共存.随着碳链长度n的增加,侧链结晶熔点Tm升高,n≥16的长碳链复合物表现出随温度变化的可逆结晶相态变化.且这类聚紫精-表面活性剂复合物表现出高于200℃的热稳定性.     

Effects of Mixed Anionic-Cationic Surfactants and Alcohol on Solubilization of Water-in-oil Microemulsions

The solubilization of water in w/o microemulsions formed with mixed-surfactants containing one anionic and one cationic surfactant and alcohol was studied as a function of alkyl chain length of oil (C6 to C16), mixed-surfactant (sodium dodecyl sulfate, SDS, and cetyltrimethylammonium bromide, CTAB, or cetylpyridinium bromide CPB), and alcohol (1-butanol, 1-pentanol, 1-hexanol). The results show that the solubilization of water in microemulsion systems increases significantly with the mixed-surfactants due to the synergistic effect resulting from the strong Coulombic interactions between cationic and anionic surfactants and the solubilizing efficiency increases as the chain length or concentration of alcohol increases. With increasing the oil chain length the solubilization for water increases, decreases, and has the chain length compatibility effect when the systems contain 1-hexanol, 1-butanol, 1-pentanol, respectively. The total solubilizing capacity increases as the surfactant concentration (keep the ratio of SDS to butanol constant) increases.     

正、负离子表面活性剂混合体系溶致液晶生成的相行为

研究了烷基(C8,C12,C14)三甲基溴化铵、烷基(C12,C14)溴化吡啶与烷基(C8,C12)硫酸钠混合体系溶致液晶形成的条件与结构的变化.在高浓度的水溶液中,随着正、负离子表面活性剂摩尔比接近于1,液晶结构由六角相过渡为层状相.表面活性剂非极性链长改变,对相行为影响显著,短碳链的正、负离子表面活性剂混合体系,在等摩尔比时,体系为层状液晶或立方液晶为主,夹杂少许沉淀.随碳链增长,两类表面活性剂间的静电吸引效果表现为生成沉淀的摩尔比例范围变宽,沉淀量增多,共存的液晶相减少,甚至消失.若只改变正离子的极性头基,季胺盐比吡啶盐与烷基硫酸盐的作用要强,形成不溶物的混合摩尔比例范围更宽.     

一维CuO纳米棒的微乳-均匀沉淀耦合法制备与结构表征

以CuSO4和NH3·H2O为原料,采用微乳-均匀沉淀耦合法制备了一维CuO纳米棒。用XRD、SEM、TEM、HRTEM和FTIR对产物的结构和形貌进行了表征。结果表明:产物为单斜晶相结构的CuO纳米棒,内部具有孔洞结构,其直径为40～110nm,长度为800～3000nm。可通过改变水核比(ω)、反应物的浓度、反应时间、反应温度等条件实现对CuO纳米棒形貌和尺寸的调控。探讨了可能的反应机理,并用热分析方法考察了CuO纳米棒对高氯酸铵(AP)分解的催化作用。     

Modification of Wyoming montmorillonite surfaces using a cationic surfactant

Surfaces of Wyoming SWy-2-Na-montmorillonite were modified using ultrasonic and hydrothermal methods through the intercalation and adsorption of the cationic surfactant octadecyltrimethylammonium bromide (ODTMA). Changes in the surfaces and structure were characterized using X-ray diffraction (XRD), thermal analysis (TG), and electron microscopy. The ultrasonic preparation method results in a higher surfactant concentration within the montmorillonite interlayer when compared with that from the hydrothermal method. Three different molecular environments for surfactants within the surface-modified montmorillonite are proposed upon the basis of their different decomposition temperatures. Both XRD patterns and TEM images demonstrate that SWy-2-Na-montmorillonite contains superlayers. TEM images of organoclays prepared at high surfactant concentrations show alternate basal spacings between neighboring layers. SEM images show that modification with surfactant reduces the clay particle size and aggregation. Organoclays prepared at low surfactant concentration display curved flakes, whereas they become flat with increasing intercalated surfactant. Novel surfactant-modified montmorillonite results in the formation of new nanophases with the potential for the removal of organic impurities from aqueous media.     

Fabrication of positively charged catanionic vesicles from ion pair amphiphile with double-chained cationic surfactant

In this study, a pseudodouble-chained ion pair amphiphile, hexadecyltrimethylammonium-dodecylsulfate (HTMA-DS), was prepared from a mixture of cationic surfactant, hexadecyltrimethylammonium bromide, and anionic surfactant, sodium dodecylsulfate. Positively charged catanionic vesicles were then successfully fabricated from HTMA-DS with the addition of cationic surfactants, dialkyldimethylammonium bromide (DXDAB), including ditetradecyldimethylammonium bromide (DTDAB), dihexadecyldimethylammonium bromide, and dioctadecyldimethylammonium bromide (DODAB), with a mechanical disruption approach. The control of charge characteristic and physical stability of the catanionic vesicles through the variations of DXDAB molar fraction and alkyl chain length was then explored by size, zeta potential, and Fourier transform infrared analyses. It was found that the molecular packing and/or molecular interaction of HTMA-DS with DXDAB rather than the electrostatic repulsion between the charged vesicles dominated the physical stability of the mixed HTMA-DS/DXDAB vesicles. The presence of DTDAB, which possesses short alkyl chains, could adjust the packing of the unmatched chains of HTMA⁺ and DS^? and promote the vesicle formation. However, the weak molecular interaction due to the short chains of DTDA⁺ could not maintain the vesicle structures in long-term storage. With increasing the alkyl chain length of DXDAB, it was possible to improve the vesicle physical stability through the enhanced molecular interaction in the vesicular bilayer. However, the long alkyl chains of DODAB unmatched with those of HTMA-DS, resulting in the vesicle disintegration in long-term storage. For the formation of stable charged catanionic vesicles of HTMA-DS/DXDAB, a good match in hydrophobic chains and strong molecular interaction were preferred for the vesicle-forming molecules.     

Solubilization of two organic dyes by cationic ester-containing gemini surfactants

Solubilization of two different types of organic dyes, Quinizarin with an anthraquinone structure and Sudan I with an azo structure, has been studied in aqueous solutions of a series of cationic gemini surfactants and of a conventional monomeric cationic surfactant, dodecyltrimethylammonium bromide (DTAB). Surfactant concentrations both above and below the critical micelle concentration were used. The concentration of solubilized dye at equilibrium was determined from the absorbance of the solution at λ(max) with the aid of a calibration curve. The solubilization power of the gemini surfactants was higher than that of DTAB and increased with increasing alkyl chain length. An increase in length of the spacer unit resulted in increased solubilization power while a hydroxyl group in the spacer did not have much effect. Ester bonds in the alkyl chains reduced the solubilization power with respect to both dyes. A comparison between the absorbance spectra of the dyes in micellar solution with spectra in a range of solvents of different polarity indicated that the dye is situated in a relatively polar environment. One may therefore assume that the dye is located just below the head group region of the micelle. Attractive π-cation interactions may play a role for orienting the dye to the outer region of the micelle.