系列磺酸钠型Gemini表面活性剂的合成及表征

通过两步反应,合成了三种磺酸钠型Gemini表面活性剂6,6′-(丙基-1,3-二基双氧)双(3-壬基苯磺酸钠)(9B-3-9B)、6,6′-(正丁基-1,4-二基双氧)双(3-壬基苯磺酸钠)(9B-4-9B)和6,6′-(正戊基-1,5-二基双氧)双(3-壬基苯磺酸钠)(9B-5-9B),并讨论了反应温度和反应时间对产物产率的影响,优化了反应条件。利用傅里叶变换红外光谱仪(FTIR)、核磁共振仪(1H NMR)和元素分析仪表征产物结构,并通过DCTA21表面界面张力仪测定其在水溶液中的表面张力。结果表明:与传统表面活性剂十二烷基苯磺酸钠(SDBS)相比,Gemini表面活性剂9B-m-9B(m=3,4,5)具有更高的表面活性,其临界胶束浓度(CMC)分别为0.14、0.11、0.12 mmol·L-1,对应的表面张力-CMC分别为29.43、29.26、28.22 mN·m-1。     

甲基偶联双（壬基苯甲醚磺酸钠）的合成及性能研究

以“绿色试剂”碳酸二甲酯为原料,通过相转移催化甲基偶联双壬基酚的O-甲基化反应,合成得到中间体甲皋偶联双（壬基苯甲醚）,再经磺化、中和制得新型Genini阴离子表面活性剂——甲基偶联双（壬基苯甲醚磺酸钠）。测定了中间体和产物Gemini表面活性剂的红外光谱、质谱及核磁共振氢谱,并测定了Gemini表面活性剂的表面张力、临界胶束浓度、增溶能力、钙皂分散力、钙离子稳定性、泡沫性能、乳化力及润湿力。结果表明,与LAS相比,本文合成的新型Gemini表面活性剂具有较低的表面张力值,cmc降低约一个数最级;且钙皂分散力、钙离子稳定性、稳泡力及乳化力均优于LAS。     

新型磺基甜菜碱的合成与性能

以壬基酚、环氧氯丙烷、二甲胺及2-羟基-3-氯丙磺酸钠为主要原料合成两性表面活性剂N,N-二甲基-N-(2-羟基-3-对壬基苯氧基）丙铵基(2-羟基）丙磺基甜菜碱。通过正交试验设计优化了中间体壬基酚环氧丙基醚的合成工艺条件,并通过红外光谱对目标产物进行结构表征。采用滴体积法确定了该表面活性剂的临界胶束浓度(cmc）和临界胶束浓度下的表面张力(γ_cmc）,其值分别为9.12×10^-4 mol/L和27.87 mN/m。并考察了45 ℃下该表面活性剂的乳化性能。     

一种不对称阴离子Gemini表面活性剂的合成及表面活性研究

以α-溴代十四酸乙酯和4-癸基苯酚为原料,经Williamson醚化、磺化及皂化反应制备了一种不对称阴离子Gemini表面活性剂α-(4-癸基-2-磺基)-苯氧基十四酸钠,简写为C12CO2Na-p-C10SO3Na,考察了醚化反应条件,并用FTIR和1HNMR表征了中间体及目标产物结构。结果表明,醚化反应的最佳条件为:以N,N-二甲基甲酰胺(DMF)和甲苯作溶剂,无水K2CO3作缚酸剂,物料比n(α-溴代十四酸乙酯)∶n(4-癸基苯酚)=1.05∶1,回流反应3 h,醚化产物收率为77.2%(以4-癸基苯酚计)。采用吊片法测定了目标产物的表面活性,其表面张力最低可降至26 mN/m左右,临界胶束浓度(CMC)为3.28×10-6mol/L,比相应常规单链表面活性剂十四烷酸钠和间癸基苯磺酸钠的CMC低3个数量级,体现出Gemini表面活性剂优异的表面活性。     

以低分子量聚乙烯基苯磺酸钠为模板的聚3,4-二氧乙烯噻吩水分散体的制备及性能

通过RAFT聚合,制备了低分子量的聚乙烯基苯磺酸钠（PSS）;其次以低分子量的聚乙烯基苯磺酸钠为模板制备了聚3,4-二氧乙烯噻吩（PEDOT）：聚乙烯基苯磺酸钠（PSS）水分散体,研究了作为模板的聚乙烯基苯磺酸钠的不同分子量对PEDOT：PSS水分散体结构和性能的影响。结果显示：通过核磁氢谱（¹H NMR）表征,证明成功制备了分子量为3900,4900,9600和18300的聚乙烯基苯磺酸钠。用荧光探针法发现低分子量PSS在水中能形成胶束,临界胶束浓度在10^-6g·ml^-1左右。用四探针表面电阻测试发现,低分子量PSS为模板可明显提高PEDOT薄膜的导电性,最大提高了近3倍。用紫外可见分光光度计（UV）研究发现,以低分子量PSS为模板使PEDOT的透明性有一定的下降,这主要是由于RAFT试剂部分和PEDOT：PSS的相分离造成的。热稳定性的测试表明,低分子量PSS为模板对PEDOT的热稳定性没有明显的影响。     

甲基偶联双（烷基酚磺酸钠）型Gemini表面活性剂的合成及性能

本文采用甲醛为偶联剂对长链烷基酚进行缩合,合成了可以制备Gemini表面活性剂的疏水骨架——甲基偶联双（烷基酚）（MBA）。将MBA磺化及中和制得了Gemini表面活性剂甲基偶联双（烷基酚磺酸钠）（MBSA）。采用IR、ESI-MS验证了MBSA的结构,并测定了两种Gemini表面活性剂的表面张力、临界胶束浓度、增溶能力、润湿力、泡沫性能、乳化力、钙皂分散力及耐电解质能力。结果表明,甲基偶联双（壬基酚磺酸钠）（MBSN）的cmc为5.9×10-4mol/L,γcmc为30.0mN/m;甲基偶联双（十二烷基酚磺酸钠）（MBSD）的cmc为4.6×10-4mol/L,γcmc为32.0mN/m。其cmc均比普通表面活性剂低一个数量级;疏水基长的MBSD比疏水基短的MBSN表面活性更强,但耐电解质能力反而降低。     

新型喹啉类Gemini表面活性剂的合成及界面吸附

以6-氨基喹啉、三光气、三乙胺为原料合成了对称的喹啉脲,其与3种溴代烷进行季铵化反应合成了3种喹啉双季铵盐Gemini表面活性剂,其结构经FTIR、~1HNMR、~(13)CNMR和ESI-MS确证。对中间体喹啉脲及目标产物喹啉Gemini表面活性剂的合成条件进行了优化。合成中间体喹啉脲的最佳反应条件为:二氯甲烷为反应溶剂,n(6-氨基喹啉)∶n(三光气)=5∶1,反应时间为6 h,1,3-二-6-喹啉基脲的收率可达88%。合成喹啉类Gemini表面活性剂的最佳反应条件为:中间体喹啉脲(a)(3.2 g,10.2 mmol),DMF(15 mL)为溶剂,反应温度为110℃,n(1,3-二-6-喹啉基脲)∶n(溴代十二烷)=1∶14,反应时间为8 h,收率可达74%。对目标产物喹啉Gemini表面活性剂在三氯甲烷-水体系中的界面张力进行了测定,结果表明:喹啉Gemini表面活性剂在三氯甲烷溶液内扩散到三氯甲烷-水界面是由纯扩散吸附控制。     

Gemini表面活性剂的研究与发展方向

Gemini表面活性剂（Dimeric surfactnat）又称双子表面活性剂、孪连表面活性刺、双生表面活性荆或偶联表面活性剂,是通过一个联接基将两个传统表面活性剂分子在其亲水头基或接近亲水头基处连接在一起而形成的一类新型袭面活性剂。由于其结构的特殊性,双子表面活性剂表现出了许多常规表面活性剂所不具备的独特性能,因而具有很强的应用潜力,现在已成为胶体和界面科学的热门研究领域。 Gemini表面活性荆的研究开始于1971年。Buton等人首次合成了一类阳离子型Gemini表面活性剂：烷基-α,ω-双二烷基双甲基烷基溴化铵[CmH2m＋1N^＋（CH3）2Br^-]2（CH2）5,随后Deinega、Parrerira、Devinsky、Okahara等人相继合成。了二些不同联接基翻和不同疏水链的新季铵盐双子表面活性剂。然而,真正开始这类新型袭面活性剂的研究工作则是从20世纪90年代初开始的,这一时期,Menger,Zann、Rosen小组和其他许多化学家在此方面作了大量的研究工作;1999年,福州大学的赵剑曦对鼠外Gemini表面活性剂的研究做了系统的综述,引起了国内相关研究单位的重视。 Gemini表面活性剂的出现是激动人心的,它的发展具有无穷的魅力和挑战性。本刊特邀福州大学化学化一学院赵剑曦院长,与大家交流关于Gemini表面活性剂的研究意义和发展方向。希望与更多同仁一起推进我国Gemini表而活性剂的发展。     

羟基和酯基型Gemini双季铵盐表面活性剂在煤沥青表面的润湿特性

以自制的羟基和酯基型Gemini双季铵盐表面活性剂为研究对象,在考察其表面活性的基础上,进一步研究了表面活性剂在煤沥青表面的润湿性。研究表明,羟基型Gemini表面活性剂在煤沥青表面的接触角随疏水链长度的增长呈先减小后增大趋势,其中C₁₂-OH在煤沥青表面的润湿效果最好;对于m-n-m酯基型Gemini表面活性剂而言,接触角随疏水链长度的增长而降低。当疏水链长度一定时,m-6-m在煤沥青表面的润湿效果比m-2-m好。在一定浓度范围内,C₁₀-OH、C₁₂-OH和12-2-123种Gemini表面活性剂的表面张力与其在煤沥青表面黏附张力呈线性关系。煤沥青表面的Zeta电位随Gemini表面活性剂浓度的增大呈先增大后趋于平稳的趋势。     

专利信息 表面活性剂系列化合物

制备支化烯烃的办法、用支化烯烃生产表面活性剂的方法和表面活性剂;水包油型乳化组合物及其制备方法;新表面活性剂双（3-烷氧基烷-2-酵）硫化物、砜和亚砜;表面活性剂的回收方法;阳离子型含氟Gemini表面活性剂     

Surface Activities of Three Anionic Gemini Surfactants Derived from Cyanuric Chloride: Effect of a Branched Hydrophobic Chain

Sodium 4,6-(2-(N,N-bis-ethylhexylamino)-1,3,5-triazine-4,6-yl-amino) ethane sulfonate (IXC₈), Sodium 4,6-(2-(N,N-bis-octylamino)-1,3,5-Triazine-4,6-yl-amino) ethane sulfonate (XC₈) and 2,2′-(6,6′-(ethane-1,2-diylbis(azanediyl) bis(4-(octylamino)-1,3,5-triazine-6,2-diyl)) bis(azanediyl))diethane sulfonate (C₈-2-C₈) were synthesized from cyanuric chloride. The surface activity and application properties of these surfactants (XC₈, IXC₈ and C₈-2-C₈) were discussed. The values of CMC, γ _CMC, pC₂₀, Γ_max, and A_min calculated from surface tension measurement at 30 °C indicate that the surface activity of IXC₈, which has two branched hydrophobic carbon chains, has lower γ _CMC (26.8 mN m^?1) than the other investigated surfactants and excellent wetting ability.     

Synthesis and Performance of a Multi-Purpose Gemini Precursor and the Derivative Alkylaryl Sulfonate Gemini Surfactants

The phenol–formaldehyde condensation reaction to synthesize a gemini precursor was renewed by using high efficient and environmentally benign resin catalysts instead of protonic acids, and the conversion, yield and selectivity of the reaction were all upgraded from the 60 % by the traditional way to over 90 % by the new way. Three alkylaryl sulfonate gemini surfactants were derived from the above gemini precursor by O-methylation, sulfonation and neutralization, that is, sodium salt of sulfonated bis(2-hydroxy-5-nonylphenyl)methane (SBHNM), sodium salt of sulfonated bis(2-hydroxy-5-dodecylphenyl)methane (SBHDM) and sodium salt of sulfonated bis(2-methoxy-5-nonylphenyl)methane (SBMNM). And their performances in aqueous solution were further investigated. The results show that the three gemini surfactants exhibit higher effectiveness and efficiency in surface tension reduction than a monomeric reference surfactant sodium dodecylbenzene sulfonate (SDBS). Furthermore their critical micelle concentration values are at least one order of magnitude lower than that of SDBS. It is also shown that O-methylation of the hydroxyl group in the gemini precursor is effective at improving the surface activity of the gemini surfactants, such as efficiency in surface tension reduction, foam stability and calcium stability. It is suggested that the synthesized hydrophobic skeleton could be a multi-purpose gemini precursor from which various gemini surfactants could be derived by further hydrophobic or hydrophilic modification.     

Synthesis of New Salt‐Resistant Sulfonate Gemini Surfactants with Hydroxyl Groups

Though the gemini surfactants have unique properties, their high cost limits their scope of application. The new salt‐resistant sulfonate gemini surfactants disodium 5,12‐bis(alkyloxymethyl)‐4,7,10,13‐tetraoxa‐2,15‐dihydroxyhexadecane 1,16‐disulfonates bearing two alkyl chains, two hydroxyl and two sulfonate groups were prepared from fatty alcohol, epichlorohydrin, glycol, sodium hydroxide, sodium bisulfite and sodium sulfite. Their synthesis exhibited the advantages of low raw material cost, mild reaction conditions and easy operation. The structures of prepared compounds were confirmed by FTIR and ¹H NMR. These gemini surfactants show excellent surface‐active properties, good salt resistance and excellent foaming ability.     

支链烷基苯磺酸钠的表征及表面性质的测定

为了研究支链烷基苯磺酸钠的构效关系,以苯为初始原料经酰化、格氏反应、氢化还原、磺化中和等4步合成了4种支链烷基苯磺酸钠。支链总碳原子数为16,苯环连接位置分别在支链的2,4,6和8位。它们的结构分别为:(A)CH3(CH2)13CH(CH3)C6H4SO3Na;(B)CH3(CH2)11CH(C3H7)C6H4SO3Na;(C)CH3(CH2)9CH(C5H11)C6H4SO3Na;(D)CH3(CH2)7CH(C7H15)C6H4SO3Na。经核磁和红外光谱确定了化合物的结构,用两相滴定方法确定了产物中烷基苯磺酸钠的质量分数均大于99%。用Wilhelmy-Plate法测定了4种支链烷基苯磺酸钠在30℃下的临界胶束浓度CMC(mmol/L)以及临界胶束浓度下的表面张力γCMC(mN/m)。CMC和γCMC值分别为:(A)0 112,35 96;(B)0 232,35 05;(C)0 420,33 86;(D)0 708,31 47。根据Gibbs吸附公式求出饱和吸附量Γm、饱和吸附面积Am以及表面压πCMC。发现随着苯环在烷基链上连接位置由2变化到8,CMC增大,γCMC降低。采用电导法测定了4种支链烷基苯磺酸钠的临界胶束浓度,其结果与表面张力法的测定结果一致。采用两种基于辛醇/水分配系数的方法预测了4种表面活性剂的CMC,结果表明,考虑了支链化的CMC与实验结果符合较好。     

Gemini Pyridinium Surfactants: Synthesis and Their Surface Active Properties

New pyridinium Gemini surfactants have been synthesized by esterification of renewable fatty acids with halogenated alcohols furnishing respective esters (2‐chloroethyl hexadecanoate, 2‐chloroethyl tetradecanoate, 2‐chloroethyl dodecanoate, 2‐bromoethyl hexadecanoate, 2‐bromoethyl tetradecanoate and 2‐bromoethyl dodecanoate) followed by their subsequent treatment with 4,4′‐trimethylenedipyridine resulting into the formation of title Gemini surfactants: (4,4′‐(propane‐1,3‐diyl)bis(1‐(2‐(hexadecanoyl oxy) ethyl) dipyridinium chloride(7), (4,4′‐(propane‐1,3‐diyl)bis(1‐(2‐(tetradecanoyl oxy) ethyl) dipyridinium chloride (8), 4,4′‐(propane‐1,3‐diyl)bis(1‐(2‐(dodecanoyl oxy) ethyl) dipyridinium chloride (9), (4,4′‐(propane‐1,3‐diyl)bis(1‐(2‐(hexadecanoyl oxy) ethyl) dipyridinium bromide (10), (4,4′‐(propane‐1,3‐diyl)bis(1‐(2‐(tetradecanoyl oxy) ethyl) dipyridinium bromide (11), 4,4′‐(propane‐1,3‐diyl)bis(1‐(2‐(dodecanoyl oxy) ethyl) dipyridinium bromide (12). Their identifications are based on IR, ¹H‐, ¹³C‐NMR, DEPT, COSY and mass spectral studies. Their surface active properties are also evaluated on the basis of surface tension and conductivity measurements and thermal stability of these long chain cationics Gemini surfactants have been measured by thermal gravimetric analysis under nitrogen atmosphere.     

Enhanced Mn2+ solidification and NH4+-N removal from electrolytic manganese metal residue via surfactants

Electrolytic manganese metal residue (EMMR) harmless treatment has always lacked a low-cost and quick processing technology. In this study, surfactants, namely tetradecyl trimethylammonium chloride (TTC), sodium dodecyl benzene sulfonate (SDBS), sodium lignin sulfonate (SLS), and octadecyl trimethylammonium chloride (OTC), were used in the solidification of Mn²⁺ and removal of NH₄⁺-N from EMMR. The Mn²⁺ and NH₄⁺-N concentrations under different reaction conditions, Mn²⁺ solidification and NH₄⁺-N removal mechanisms, and leaching behavior were studied. The results revealed that the surfactants could enhance the Mn²⁺ solidification and NH₄⁺-N removal from EMMR, and the order of enhancement was as follows: TTC > SDBS > OTC > SLS. The NH₄⁺-N and Mn²⁺ concentrations were 12.3 and 0.05 mg·L^-1 with the use of 60.0 mg·kg^-1 TTC under optimum conditions (solid–liquid ratio of 1.5:1, EMMR to BRM mass ratio of 100:8, temperature of 20 ℃, and reaction duration of 12 h), which met the integrated wastewater discharge standard (GB8978-1996). Mn²⁺ was mainly solidified as Mn(OH)₂, MnOOH and MnSiO₃, and NH₄⁺-N in EMMR was mostly removed in the form of ammonia. The results of this study could provide a new idea for cost-effective EMMR harmless treatment.     

Novel 4-amino bis-pyridinium and bis-quinolinium derivatives as choline kinase inhibitors with antiproliferative activity against the human breast cancer SKBR-3 cell line

Choline kinase (ChoK) is the first enzyme in the CDP-choline pathway that synthesizes phosphatidylcholine, the major phospholipid in eukaryotic cell membranes. Human ChoK has three isoforms: ChoKα1, α2, and β. Specific inhibition of ChoKα has been reported to selectively kill tumor cells. In this study, ten new symmetrical bis-pyridinium and bis-quinolinium derivatives were synthesized and tested for their ability to inhibit human ChoKα2. These compounds have electron-releasing groups at position 4 of the pyridinium or quinolinium rings. 1,1'-[(Butane-1,3-diylbis(benzene-1,4-diylmethylene)]bis[4-(4-bromo-N-methylanilino)pyridinium)] dibromide and 1,1'-(biphenyl-3,3'-diylmethylene)bis[7-chloro-4-(perhydroazepine-1-yl)quinolinium] dibromide were identified as highly potent ChoK inhibitors with IC(50) values of 80 nM. Kinetic enzymatic assays indicated a mixed and predominantly competitive mechanism of inhibition for these compounds, which exhibited strong antiproliferative activity (EC(50) 1 μM) against the human breast cancer SKBR3 cell line.     

Mie scattering of electromagnetic radiation by a sphere: A computer program

A computer program for calculating the Mie scattering of electromagnetic radiation by a sphere is described. The program will evaluate, amongst other parameters, the Mie scattering functions a_m and b_m, the extinction, scattering, back-scattering, absorption and radiation pressure efficiencies, the intensity functions, I₁ and I₂ and the polarisation ratios

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. The program can be made available to other users and computations can be commissioned on a repayment basis. A library of results is being established.     

About randomness of aerosol size distributions

All aerosol formation and evolution processes, such as nucleation, condensation, fragmentation, etc., are understood and rationalized via fundamental probabilistic concepts such as probabilities of collision, coagulation, dispersion, etc. Therefore all theoretical size distribution functions (lognormal, modified gamma distribution, self-preserving particle size distribution for Brownian coagulation, etc.) are in fact size probability density functions pdf(r). Any (e.g., measured) size distribution f(r) of an aerosol system is some random realization of its pertinent size probability density function pdf(r). When pdf(r) is viewed as a continuous function, the corresponding size distribution vanishes almost everywhere excluding some randomly set of sizes where f(r)=1. We investigate proximity between f(r) and pdf(r) in finite size intervals and derive expressions for estimation of the standard deviations of several aerosol size-dependent properties arising from randomness of f(r).     

Synthesis of ceria nanoparticles by flame electrospray pyrolysis

A flame electrospray pyrolysis is presented for synthesizing CeO₂ nanoparticles with a dense morphology, high crystallinity and nanometer size. Hydrated cerium nitrate precursor dissolved in an ethanol/diethylene glycol butyl ether mixture was injected into a CH₄/air premixed flame using an electrospray method. The number size distributions of the as-prepared particles were trimodal. It is suggested that the particles for the fine mode were formed by a Rayleigh disintegration of the charged precursor droplets during the droplet evaporation. The particles for the coarse and middle modes are surmised to come from primary and secondary droplets, respectively, which were formed simultaneously during the atomization processes. The CeO₂ nanoparticles for the coarse mode were nonspherical and composed of few crystallites. The nanoparticles for the fine and middle modes were nearly spherical and nonagglomerated. The as-prepared CeO₂ nanoparticles showed highly crystallinity.