Chitosan and multi-walled carbon nanotube composite rods

<正>Multi-walled carbon nanotubes(MWNTs) and chitosan(CS) composite rods with layer-by-layer structure were prepared via in situ precipitation method.On the one hand,some MWNTs fragments with open tips played the role of nuclear agent to improve the crystallinity of CS.On the other hand,MWNTs embedded in CS matrix to absorb energy when the composite rods were destroying.Nanotubes pulled out from CS matrix,and lots of holes remained,so MWNTs could endure external stress effectively.The bending strength and bending modulus of CS/MWNTs rods(100/0.5,W/W) arrived at 130.7 MPa and 4.4 GPa respectively,increased by 34.3%and 7.3%compared with those of pure CS rods.Consequently, CS/MWNTs composite rods with excellent mechanical properties could be a novel device used for bone fracture internal fixation.     

Rheology of novel self-thickening cationic gemini surfactant solutions

A new cationic Gemini surfactant (25-HP-25) was synthesized with eruamidopropyl dimethylamine and epichlorohydrin, and its solution is self-thickening. The rheological properties of 25-HP-25 and 3-chloro-2-hydroxypropyl eruamidopropyl dimethyl ammonium acetate (EDAA) solutions were compared. The solution of EDAA behaves as Newtonian fluid (1?s^?1??1). Whereas the 25-HP-25 micelle solution (2?wt%) exhibits higher viscosity, which is about three hundred times than that of EDAA solution at low shear rate (γ??1). Especially, the 25-HP-25 solution shows obvious thixotropy, and with the increase of concentration, the viscoelasticity becomes better. Furthermore, the compaction of network structures has been confirmed by cryo-field emission scanning electron microscopy (cryo-FESEM) micrographs. This work is expected to enrich the research field of self-thickening surfactant.     

Membrane electrodes sensitive to doubly charged surfactants. Application to a cationic gemini surfactant

The response of a membrane electrode is not always identical to that of a redox electrode. Indeed, in the case of membrane electrode the response is not due to a redox equilibrium but to a cross-membrane potential. So, the membrane electrode's response depends mainly on the carrier system and the nature of the membrane. The properties of the membrane can favour several reactions giving rise to different ionic species diffusing in the membrane. The expression of the cross-membrane potential thus depends on the number and quantities of these ionic species. To illustrate this, we established the equations for the case of a two-charge cation detected by a univalent charged carrier. We show that the Nernstian response is not applicable to membrane electrodes. This approach allowed us to interpret results obtained with a cationic gemini surfactant-selective electrode prepared in the laboratory. To prove the well working of this electrode, we determined the critical micelle concentration in water and several NaBr solutions (0.004, 0.006, 0.01 and 0.02 M) from which the counterion binding has been determined.     

Aqueous two-phase system of an anionic gemini surfactant and a cationic conventional surfactant mixture

The aqueous two-phase system formed by the mixture of dodecyltrimethylammonium bromide (DTAB) with a gemini surfactant O,O′-bis(sodium 2-lauricate)-p-benzenediol (C₁₁pPHCNa) has been studied. Two two-phase regions were observed, one was a wide region in the cationic surfactant-rich side and the other in the vicinity of R = 1:1, where R is the mixing mole ratio of DTAB to C₁₁pPHCNa in global solution. Multi-lamellar vesicles are formed in the concentrated upper phase of cationic surfactant-rich systems and spherical aggregates in the concentrated bottom phase at R = 1:1. The microstructure of the solution and the phase behavior of the aqueous two-phase system strongly depended on the total concentration and the composition of the system.     

Micellar-catalyzed alkaline hydrolysis of 2,4-dinitrochlorobenzene in a cationic gemini surfactant

Micellar-catalyzed alkaline hydrolysis of 2,4-dinitrochlorobenzene (DNCB) in the presence of a conventional cationic surfactant CTAB or a cationic gemini surfactant 1,2-ethane bis(dimethyldodecylammonium bromide) (12-2-12) were studied spectrophotometrically at 25 °C. It was found that both CTAB and 12-2-12 micelles accelerated the alkaline hydrolysis of DNCB, and the binding constant of the substrate to the micelle, K_S, for 12-2-12 (K_S = 310 M⁻¹) was larger than that for CTAB (85 M⁻¹), which suggested that DNCB molecules bound with gemini micelles more easily than with CTAB. However, the second-order rate constant in micellar pseudophase (k_M = 1.22 × 10⁻³ s⁻¹) for 12-2-12 was lower than k_M for CTAB (4.01 × 10⁻³ s⁻¹) because the substrate may enter the interior of the 12-2-12 micelles. It was found also that 12-2-12 had a similar catalysis mechanism to CTAB when the concentration of 12-2-12 was relatively low (ca. <5 mM). However, above this concentration, higher microviscosity and significant increases in aggregation number and micelle size with increased surfactant concentration may remarkably influence the hydrolysis reaction.     

Phase-transfer catalysis of a new cationic gemini surfactant with ester groups for nucleophilic substitution reaction

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.     

C12-m-C12型阳离子Gemini表面活性剂在煤沥青表面的润湿性

利用座滴法和电泳法研究了阳离子Gemini表面活性剂C₁₂-m-C₁₂·2Br^-(m=4、6、8、10)在煤沥青表面的润湿性质及吸附机理。结果表明, 表面张力均随表面活性剂浓度的增大而减小, 超过临界胶束浓度(CMC)后趋于平稳, 接触角θ和铺展系数S的变化趋势与表面张力类似; 在所研究浓度范围内,C₁₂-10-C₁₂型表面活性剂的γ_lg~cosθ曲线符合Zisman理论, 且侵湿功(W_i)与表面张力也呈线性关系; 煤沥青表面的Zeta电位随表面活性剂浓度的增加从负电变为正电,最后趋于平稳, 且零电位对应的浓度比CMC至少低一个数量级; C₁₂-8-C₁₂型Gemini表面活性剂能显著改变煤沥青表面的润湿性. 由Gemini表面活性剂在煤沥青表面润湿结果及Zeta电位可以看出, C₁₂-m-C₁₂型Gemini表面活性剂在煤沥青表面的润湿是静电作用和范德华吸附共同作用的结果; 润湿过程可分为三个阶段。     

多壁碳纳米管固相萃取填料对芳香化合物的吸附机理研究

研究了多壁碳纳米管(MWNT)作为固相萃取柱填料对芳香有机化合物的吸附性能,并探讨了吸附作用的本质。采用MWNT分别萃取了不同结构的物质,实验结果表明,MWNT对芳香有机化合物有较强的吸附作用,这种作用主要是由于MWNT表面的离域大π键和芳香环的共轭π键相互作用的结果,而碳纳米管的高比表面积产生的物理吸附作用相对要小得多。     

Isothermal crystallization kinetics and thermal behavior of poly(?-caprolactone)/multi-walled carbon nanotube composites

This study describes the preparation of poly(?-caprolactone) (PCL)/multi-walled carbon nanotube (MWCNT) composites by ultrasonically mixing the PCL and as-fabricated MWCNT in a tetrahydrofuran solution. The TEM images show that the MWCNT is well separated and uniformly distributed in the PCL matrix. Differential scanning calorimetry (DSC), thermogravimetric analyzer (TGA), X-ray diffraction (XRD) and polarized optical microscopy (POM) were used to investigate the isothermal crystallization kinetics, crystalline structure and thermal behavior of PCL and PCL/MWCNT nanocomposites. DSC isothermal results revealed that the activation energy of PCL extensively decreases with increasing MWCNT contents, suggesting that the loading of MWCNT into PCL matrix probably induced heterogeneous nucleation during crystallization processes. From TGA data, the addition of small amount of MWCNT into PCL matrix can improve the thermal stability of PCL matrix. TGA isothermal degradation data illustrate that the activation energy E_d of the composites is smaller than that of PCL. This phenomenon can be attributed to the incorporation of more MWCNT loading into PCL caused a decrease in the degradation rate and an increase in the residual weight for PCL/MWCNT nanocomposites.     

多巴胺和抗坏血酸在十六烷基三甲基溴化铵/碳纳米管电极上的检测

研究了十六烷基三甲基溴化铵(CTMAB)/多壁碳纳米管修饰玻碳电极的制备以及多巴胺和抗坏血酸在该修饰电极上的电化学行为。在CTMAB和多壁碳纳米管的协同作用下,该修饰电极对多巴胺和抗坏血酸均具有显著的催化氧化作用,多巴胺和抗坏血酸的氧化峰电位分别为223mV和15mV,实现了在抗坏血酸共存时测定多巴胺。在pH7.0的磷酸盐缓冲溶液中,多巴胺和抗坏血酸的线性范围分别为2.0×10-6～2.0×10-3mol/L和4.0×10-5～1.0×10-2mol/L,检出限分别为6.0×10-7mol/L和1.0×10-5mol/L。     

Micellar effects of a triazole-based cationic gemini surfactant on the rate of a nucleophilic aromatic substitution reaction

The reaction between 2,4-dinitrochlorobenzene (DNCB) and hydroxide ion was studied spectrophotometrically at 25 °C in micelles of a triazole-based cationic gemini surfactant 18-triazole-18 or micelles of the conventional cationic surfactant CTAB. Both CTAB and 18-triazole-18 accelerated this nucleophilic aromatic substitution reaction. The binding constant of the substrate to the micelle, K _S, for 18-triazole-18 (K _S=335 M⁻¹) was found to be much larger than that for CTAB (85 M⁻¹) by fitting the kinetic results with pseudophase ion-exchange (PIE) model, which suggests that DNCB binds with gemini micelles more easily than it does with CTAB micelles. It was also found that 18-triazole-18 catalytic system was in accordance with PIE model at surfactant concentrations below ca. 0.5 mM, above which the increase of viscosity and the change of micelle size with increased surfactant concentration may remarkably influence the reaction. This was quite different from the reaction catalyzed by micelles of the conventional surfactant CTAB.     

茜素红S/多壁碳纳米管修饰碳糊电极阳极溶出伏安法测定痕量铜

制备了茜素红S/多壁碳纳米管修饰碳糊电极,提出了一种灵敏的溶出伏安法测定痕量铜的新方法.在极谱分析仪上采用二阶导数线性扫描伏安法进行分析,在0.1 moL/L的HAc-NaAc缓冲溶液(pH 4.1)中,Cu与修饰电极表面的茜素红S(ARS)形成Cu(Ⅱ)-ARS络合物而富集于电极表面,于-400 mV处还原后,再进行阳极化扫描,于64 mV处获得一灵敏的铜的阳极溶出峰,峰电流与Cu(Ⅱ)浓度在2×10-11 mol/L～6×10-7 mol/L范围内呈良好的线性关系,检出限(S/N=3) 为8.0×10-12 mol/L(富集时间240 s).方法应用于人发中铜含量的测定,回收率为98%～102%.     

新型腰果酚双子表面活性剂的合成及表面活性

以天然生物质腰果酚、1,3-二溴丙烷及氯磺酸为原料,通过醚化、磺化及中和三步反应合成了一类新型的腰果酚基磺酸盐双子(Gemini)表面活性剂.采用傅立叶转换红外光谱仪和核磁共振谱仪表征了产物的结构;采用滴体积法测定了腰果酚Gemini表面活性剂的表面张力,研究了水溶液的表面性质,并与相应的单基腰果酚基磺酸盐表面活性剂进行了对比.结果表明:腰果酚Gemini表面活性剂水溶液的临界胶束浓度(cmc)为6.20×10-2 mmol.L-1,远小于相应的单基腰果酚表面活性剂水溶液的cmc(8.40mmol.L-1);其临界表面张力γcmc为36.92mN.m-1,与单基腰果酚表面活性剂水溶液的相近(γcmc为38.41mN.m-1).与此同时,腰果酚Gemini表面活性剂水溶液的最小分子截面积Amin为0.27nm2,比相应的单基表面活性剂水溶液的小得多.     

Rheological and thermo-responsive characteristics of the mixed aqueous solution of gemini cationic surfactant and hydroxyl naphthalene carboxylic acid sodium

The new thermo-switchable wormlike micellar systems were developed by mixing the gemini cationic surfactant, 2-hydroxypropyl-1,3-bis (dimethylmyristylammonium chloride) (14-3(OH)-14(2Cl) and sodium 1-hydroxynaphthalene-2-carboxylate (1SHNC) and sodium 2-hydroxynaphthalene- 3-carboxylate (2SHNC) in a certain concentration range. Their viscoelastic and thermos-responsive behaviors as a function of the salts concentration or temperature were investigated via rheological and cryo-TEM investigations. The results demonstrated that the zero-shear viscosity (η₀) significantly increased while raising salt concentrations above a threshold concentration (C_S*) until reaching maximum and then decreased. For the mixed solutions before the maximum, the zero-shear viscosity linearly decreased with increasing temperature and conformed to the Arrhenius law. However, for those mixed systems displaying thermo-responsive characteristic after the summit, the curve of η₀ as a function of temperature exhibited a maximum over the whole temperature range, namely, the systems showed thermo-thickening and thermo-thinning behaviors at low and high temperatures. The abovementioned phenomena were explained by the formation of hydrogen bond in 14-3(OH)-14(2Cl) molecules and the different solubility of SHNC under different temperatures, and the transition mechanisms of the aggregates were analyzed accordingly.     

Modification of carbon paste with congo red supported on multi-walled carbon nanotube for voltammetric determination of uric acid in the presence of ascorbic acid

A chemically modified carbon-paste electrode (CPE) is prepared by incorporating congo red (CR) immobilized on multi-walled carbon nanotube (MWCNT). The results show that CR is effectively immobilized on the surface of MWCNT under the ultrasonic agitation in aqueous solution and further incorporating the nafion. The prepared electrode, due to the electrostatic repulsions between the CR and ascorbate anion, is capable to mask the response of the ascorbic acid (AA) completely and provide an effective method for the detection of minor amounts of uric acid (UA) in the presence of high concentrations of AA. On the other hand, an increase in the microscopic area of the electrode by addition of MWCNT together with the electrocatalytic activity caused to a significant enhancement in the voltammetric response to UA. Optimization of the amounts of composite modifier in the matrix of CPE is performed by cyclic and differential pulse voltammetric measurements. The modified electrode shows a linear response to UA in the range of 1.0 × 10⁻⁷–1.0 × 10⁻⁴ M with a detection limit of 1.0 × 10⁻⁸ M. The electrode exhibits excellent accuracies for the determination of UA in the presence of high concentrations of AA (a recovery of 97.6%). The response of the electrode toward sulfhydryl compounds such as cysteine, penicillamine, and glutathione is not considerable. This reveals a good selectivity for the voltammetric response toward UA. The effective electrocatalytic property, ability for masking the voltammetric responses of the other biologically reducing agents, ease of preparation, and surface regeneration by simple polishing together with high reproducibility and stability of the responses make the modified electrode suitable for the selective and sensitive voltammetric detection of sub-micromolar amounts of UA in clinical and pharmaceutical preparations.     

An enhanced electrocatalytic oxidation and determination of 2,4-dichlorophenol on multilayer deposited functionalized multi-walled carbon nanotube/Nafion composite film electrode

The voltammetric (CV and DPV) behavior of multi-walled carbon nanotube/Nafion composite coupled with a glassy carbon electrode was investigated for the determination of 2,4-dichlorophenol. The structural and morphological evaluation by XRD and FESEM revealed that the acid treated MWCNT retained their morphology without any structural change. The existence of the possible functional groups was investigated by FTIR and Raman spectroscopy. Compared to bare GCE, a significantly reduced interfacial charge transfer resistance was noticed for MWCNT/Nafion/GCE by electrochemical impedance spectroscopy (EIS). The use of Nafion not only contributed to the non-covalent functionalization of MWCNT, but also protected the electrode surface against the polymerization of phenoxy radicals forming a passivating film. For MWCNT/Nafion/GCE, the combination of anti-passivating ability and excellent catalytic properties resulted in the rapid and direct electrochemical determination of 2,4-DCP. Under optimal experimental conditions, the DPV responses for MWCNT/Nafion/GCE is linear over the 1–150 μmol/L range with a detection limit (S/N = 3) of 0.01 μmol/L. The presence of many interfering species had no influence on the signals of 2,4-DCP. The proposed sensor was successfully tested for the determination of 2,4-DCP in tap water samples and the recovery was in the range of 99.0–102.5%.     

聚吡咯／多壁碳纳米管修饰电极对多巴胺的测定

制备了聚吡咯/多壁碳纳米管(PPy/MWNT)复合膜修饰电极。研究了神经递质多巴胺(DA)在该修饰电极上的电化学行为。实验表明,PPy/MWNT复合膜修饰电极对DA的电催化作用优于PPy修饰电极。在pH=4.10的0.2mol/L醋酸-醋酸钠缓冲溶液中,DA在该修饰电极上的CV曲线于0.31V和0.28V处出现一对灵敏的氧化还原峰,峰电位差△Ep比裸玻碳电极降低58mV,比PPy修饰电极降低28mV,峰电流显著增加。氧化峰电流ipa与DA浓度在1.0×10-4~7.8×10-8mol/L范围内呈良好的线性关系,线性回归方程为ip(μA)=0.2512 1.2300C(×10-5mol/L),相关系数r=0.9992,检出限为3.9×10-8mol/L。常见物质对DA的检测无干扰,DA注射液样品检测回收率为94%~104%。     

Electro-deposition of platinum nanoparticles on 4-mercaptobenzene-functionalized multi-walled carbon nanotubes

A new method to electro-deposit platinum nanoparticles on the surface of multi-walled carbon nanotubes (MWNTs) functionalized with 4-mercaptobenzene has been described. X-ray photoelectron spectroscopy results reveal that 4-mercaptobenzene was attached to the surface of MWNTs. Transmission electron microscope and X-ray diffraction analysis confirm that platinum nanoparticles were highly dispersed on the surface of MWNTs, and the average size of the platinum particle is 4.2 nm. The electrocatalytic properties of the Pt/MWNT composite electrode for methanol oxidation were investigated by cyclic voltammetry, and the results show that the fabricated composites exhibit high catalytic activity and good long-term stability. The study provides a feasible approach to fabricate Pt/MWNT composite electrode for direct methanol fuel cell.     

多壁碳纳米管负载TiO2的光催化脱硝性能

采用溶胶凝胶法制备了多壁碳纳米管负载TiO₂ （MWCNTs/TiO₂）,并利用透射电镜、X射线光电子能谱、X射线衍射和紫外-可见漫反射光谱对样品进行了表征。结果表明,MWCNTs/TiO₂晶型以锐钛矿为主,MWCNTs的引入会限制TiO₂晶粒的生长。另外,MWCNTs/TiO₂的光吸收边向长波区域偏移。针对模拟烟气,在固定床光催化反应器中对采用涂覆处理的MWCNTs/TiO₂的光催化脱硝性能进行了实验研究。结果表明,NO初始浓度较低时,光催化脱硝效率较高,SO₂的存在可抑制光催化脱硝过程,而O₂及H₂O则有促进作用。在最佳实验条件（73 mg/m³ NO,8% O₂,5% H₂O）下,光催化脱硝效率可达46%。提出了光催化脱硝反应机理。