磷酸酯甜菜碱两性表面活性剂的合成与性能

磷酸酯甜菜碱从皮肤溶出的氨基酸量少,脱脂低,毒性和刺激性低,易降解,是一类性能优良两性表面活性剂[1,2]。它的合成大多以长链卤烷或胺为原料,成本较高。本文以高级脂肪醇、氯乙醇以及二甲胺为原料、P2O5为磷酸化剂,合成了C12H25OCH2CH(OOCCH3)CH2N+(CH3)2CH2CH2OP(O)(O )(OH)磷酸酯甜菜碱。测定了表面张力、泡沫性能、钙皂分散力及增溶能力。1　合成十二烷基缩水甘油醚(Ⅰ)[2]　在500ml三颈烧瓶中加入月桂醇0 2mol,正已烷200ml和四丁基溴化铵0 01mol;在室温和强烈搅拌下加入50%的NaOH水溶液48g,滴加环氧氯丙烷0 4mol后升…     

一种含1,3,5-三嗪环的六臂引发核的合成与表征

三聚氯氰由于分子中的均三嗪环热、氧稳定性良好,并且具有光活性和生物活性[1-2],分子中的三个氯原子具有类似酰氯的反应活性,并且可以通过控制温度达到分步取代:第一个氯原子取代温度在0～10℃,第二个氯原子在25～35℃开始反应,第三个在80～90℃开始反应[3].     

Multiple BODIPY derivatives with 1,3,5-triazine as core: balance between fluorescence and numbers of BODIPY units

The multiple BODIPY derivatives could exhibit higher fluorescence than mono-BODIPY derivatives but also might produce the stronger aggregation-induced quenching effect. It is important to investigate the relationship between fluorescence and numbers of BODIPY units. In this work, series of multiple BODIPY derivatives 2–5 with 1,3,5-triazine as core were designed and synthesized in high yields. A subtle balance between the fluorescence enhancement of multiple BODIPY units and fluorescence quenching based on H-aggregation of multiple BODIPY units was observed for these multiple BODIPY derivatives. Compound 3 bearing two BODIPY units with triazine as core presented the strongest fluorescence emission and highest fluorescence quantum yield. Compound 3 was successfully applied in viscosity measurement, exhibiting the linear relationship between fluorescence intensity (or steady-state emission anisotropy) and viscosity.     

基于胱氨酸的Gemini型表面活性剂的合成及其性质

合成了基于胱氨酸的两种Gemini表面活性剂, N,N’-二对丁氧基肉桂酰胺基胱氨酸钠(SDBCC)和N,N’-二癸酰胺基胱氨酸钠(SDDC). 利用表面张力、动态光散射(DLS)、透射电镜(TEM)等手段研究了体系的表面性质和聚集行为.     

Synthesis and photophysical properties of hyperbranched polyfluorenes containing 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine as the core

A series of new hyperbranched polymers containing a 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine core unit and polyfluorene chain arms have been synthesized via Suzuki coupling, and characterized by NMR, IR and GPC. All the polymers exhibit good thermal stability with a high decomposition temperature. By changing the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine/fluorene ratio the UV-vis absorption and emission spectra can be partially tuned. It has been found that the polymers containing a low ratio of 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine units (P1-P3) have an absorption maximum around 385 nm, localized in the polyfluorene chain, and a shoulder around 425 nm ascribable to a charge transfer state involving the fluorene and the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine core. Increasing the molar ratio of the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine unit enhances the charge transfer band which becomes dominant for P4. The LUMO level of these polymers is relatively low due to the electron affinity of the triazine group. The polymers show dual emission, with a structured band in the blue (410-440 nm), attributed to the polyfluorene, and a broad band in the red (470-500 nm) associated with the charge transfer state. All the polymers exhibit two-photon absorption activity in the range of 660 to 900 nm with the maximum two-photon absorption (TPA) cross-section red-shifted from the corresponding linear absorption. The values of the TPA cross-sections vary from 1000 to 5000 GM, following the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine/fluorene ratio.     

Complexation of DNA with cationic surfactants as studied by small-angle X-ray scattering

The phase behaviors of the complex formed by didodecyldimethylammonium bromide(DDAB)and cetyltrimethylammonium bromide(CTAB)interacting with three different types of DNAs,salmon testes DNA(~2000 bp),21-bp double-stranded oligonucleotides(oligo-ds DNA),and 21-nt single-stranded oligonucleotides(oligo-ss DNA)were studied by synchrotron small-angle X-ray scattering.It was found that the DNA length and flexibility,together with the positive/negative charge ratio,determined the final structure.At higher charge ratios,the DNA length exhibited negligible effect.Both oligo-ds DNA and salmon DNA formed inverted hexagonal packing of cylinders with CTAB,as well as bilayered lamella with DDAB.However,at lower charge ratios,oligo-ds DNA formed a distorted hexagonal phase with CTAB and a new structure with DDAB,which was different from the behaviors of salmon DNA.The flexible oligo-ss DNA formed rich structures that were subject to environmental disturbance.Kinetic study also indicated that the structures of the complex formed by oligo-ss DNA took much longer to mature than the structures formed by oligo-ds DNA.We attributed this result to the conformational adjustment of oligo-ss DNA in the complex.     

Synthesis and central nervous system stimulant activity of 5,8-methanoquinazolines fused with imidazole,thiadiazole, pyrimidine and 1,3,5-triazine

5,8-Methanoquinazolines fused with imidazoles 4a-4b , thiadiazoles 5–6 , pyrimidines 7, 9, 11 and 12 , and 1,3,5-triazine 13 were prepared starting from (5R,8S)-2-amino-8,9,9-trimethyl-5,6,7,8-tetrahydro-5,8-methanoquinazoline 3 . Most compounds possessed central nervous system stimulant activities.     

Synthesis and solution properties of sulfate-type hybrid surfactants with a benzene ring

Nine novel sulfate-type hybrid surfactants, C_mF_2m+1C₆H₄CH(OSO₃Na)C_nH_2n+1 (FmPHnOS: m=4, 6, 8; n=3, 5, 7; C₆H₄: p-phenylene), with a benzene ring in their molecules were synthesized. Alkanoyl chlorides were allowed to react with iodobenzene in the presence of aluminum chloride to give the corresponding aromatic ketones. The reaction of the ketones with perfluoroalkyl iodides yielded 1-[4-(perfluoroalkyl)phenyl]-1-alkanones as intermediates. The intermediates were allowed to react with methanol in tetrahydrofuran in the presence of sodium borohydride to yield 1-[4-(perfluoroalkyl)phenyl]-1-alkanols. The desired hybrid surfactants were obtained by the reaction of 1-[4-(perfluoroalkyl)phenyl-1-alkanols with sulfur trioxide/pyridine complex in pyridine and by the subsequent neutralization of the products with sodium hydroxide solution. When compared with the conventional hybrid surfactants, C_mF_2m+1C₆H₄COCH(SO₃Na)C_nH_2n+1 (FmHnS: m=4, 6; n=2, 4, 6; C₆H₄: p-phenylene), the new hybrid surfactants thus synthesized were found to have a comparable ability to lower the surface tension of water and a high hydrophilicity. The cmc of FmPHnOS obeyed Kleven’s rule and their occupied areas per molecule increased with increasing m and n with the values between 0.66 and 1.05 nm². The aggregation number for FmPHnOS micelles ranged from 6 to 45 and the hydrodynamic radius of the micelles was in the range of 1.4-3.1 nm.     

Head group specificity of novel functionalized surfactants: synthesis,self-assembly and calcium tolerance

The present work describes the synthesis, characterization and application of functionalized surfactants derived through simple organic reaction steps. These surfactants have been particularly tailor made to resist hardness due to calcium ions in water. It is unique of its kind because here the surfactants have an analogous hydrophobic chain but differ structurally in the composition of the head groups in terms of the position of attachment of the chain. The effect of this small variability in the head group on the surfactant property, adsorption, self assembly and calcium tolerance behaviour has been studied in detail. This kind of phenol–keto surfactants has not been reported before. It was also found that one of the surfactants was more tolerant towards Ca²⁺ ion than the other. The individual packing behaviour of the surfactants at the air–water interface has been projected to cause this difference which is very interesting.     

丙烯酰胺型阴离子表面活性单体的化学结构与其胶束化行为

对两种丙烯酰胺型阴离子表面活性单体(2-丙烯酰胺基十四烷磺酸钠, NaAMC₁₄S; 2-丙烯酰胺基十二烷磺酸钠, NaAMC₁₂S)的化学结构与胶束化行为的关系进行了较深入的研究. 使用紫外分光光度法测定了NaAMC₁₄S, NaAMC₁₂S及十二烷基磺酸钠(SDS)在水中的溶解度, 同时采用表面张力法(环法)测定了它们在不同温度下的临界胶束浓度CMC; 采用稳态荧光探针法测定了不同浓度的胶束聚集数与本征胶束聚集数. 实验结果表明, 与普通表面活性剂相比, 由于丙烯酰胺型阴离子表面活性单体分子中具有两个亲水头基, 在水中的溶解性能较强, 故具有较低的Krafft温度; 在溶液表面的饱和吸附量低, 故降低水表面张力的能力较差, 即表面活性差; 疏水缔合的胶团较为疏松, 故聚集数很小; 胶束内分子间的疏水相互作用较弱, 故临界胶束浓度CMC较高.     

A comparative study on the cooperative binding of surfactants with solubilized polymers and networks

The cooperative binding of a linear as well as a crosslinked polyelectrolyte with an oppositely charged surfactant has been analyzed theoretically and experimentally. The experimental results showed that the presence of crosslinkage significantly enhances the initiation process but strongly suppresses the cooperation of the binding. In the theoretical analysis, the hydrophobic interaction has been treated using the nearest-neighbor interaction model, while the electrostatic interaction has been calculated using a rodlike model. The general formulas derived on the basis of the free energy minimum principle demonstrated that the crosslinkage enhances the initiation process but strongly suppresses the cooperation owing to the osmotic pressure in the network domain. The theoretical results showed fairly good agreement with the experimental data, confirming the essential features of the theory.     

Novel fluorescent liquid crystals: synthesis,mesomorphism and fluorescence of triphenylene-Bodipy derivatives based on 1,3,5-triazine core

The novel triphenylene-Bodipy derivatives 6 and 7 based on 1,3,5-triazine core were designed and synthesised by introducing BODIPY unit and triphenylene units sequentially onto cyanuric chloride. The Bodipy derivative 6 with one triphenylene unit was a nematic liquid crystal but the derivative 7 with two triphenylene units was a hexagonal columnar liquid crystal. The investigation on photophysical properties suggested that both of them exhibited excellent fluorescence with high fluorescence quantum yields and the Stokes shifts were larger than their Bodipy precursors. This research presented a good example of design and synthesis of columnar Bodipy liquid crystal with high fluorescence and large Stokes shift.     

Comparative study on the interaction of DNA with three different kinds of surfactants and the formation of multilayer films

The interactions between double-stranded DNA (dsDNA) and three different kinds of surfactants, i.e., cationic, anionic, and nonionic surfactants, were investigated by cyclic voltammetry, electrochemical impedance spectroscopy and UV-vis spectroscopy. Multilayer films composed of DNA and surfactants were prepared at gold electrode by electrostatic or hydrophobic interactions. It was found that the cationic surfactant, CTAB, can bind to DNA by electrostatic interaction, and the electron transfer resistance of CTAB-DNA complex film increases first and then decreases with CTAB concentration. The anionic surfactant, LAS, can bind to DNA but by hydrophobic interaction, and the electron transfer resistance of the complex film keeps decreasing with LAS concentration. Nonionic surfactants can also directly bind to DNA by hydrophobic interaction. All the three different kinds of surfactants can form multilayer films with DNA on the electrode surface. The chemical structure of DNA keeps unchanged during interacting with these surfactants. The binding modes of DNA with these three different kinds of surfactants were also deduced.     

Synthesis of novel twisted carbazole-quinoxaline derivatives with 1,3,5-benzene core: bipolar molecules as hosts for phosphorescent OLEDs

A series of carbazole/quinoxaline hybrids have been synthesized by classic Ullmann and Pd/Cu-catalyzed Sonogashira coupling reaction. Their photophysical, thermal, and electrochemical properties were investigated. The introduction of electron rich carbazole and electron deficient quinoxaline on to the 1,3,5-benzene center leads to a twisted structure with good glass forming property and imparts a bipolar character. The triplet energies in the range of 2.34-2.53 eV indicate them as potential host materials in phosphorescent OLEDs.     

Liquid crystal-forming aqueous hydroxypropyl cellulose solutions: Effects of surfactants on the turbidity and shear viscosity

The effects of type and concentration of surfactant on the turbidity and viscometric behavior for dilute and concentrated aqueous hydroxypropyl cellulose (HPC) solutions were examined. Two anionic surfactants, sodium dodecyl benzene sulfonate (SDBS) and sodium dodecyl sulfate (SDS), caused the cloud point of the dilute system to increase, but a nonionic and two cationic surfactants did not do so markedly. The transmittance for the dilute system increased with surfactant. The transmittance and viscometric behavior for the concentrated system were strongly dependent on the phase of the system: In the single-phase (isotropic and anisotropic), the transmittance and viscosity increased with SDBS, but, in the biphasic region, the behaviors were not as simple. An attempt was made to explain the transmittance and viscometric behavior in the single-phase on the basis of the change in apparent molecular weight and in order of HPC molecules. The phase transformation appeared to become less sensitive to temperature with SDBS. © 1993 John Wiley & Sons, Inc.     

锰为中心原子的三元杂多配合物的合成与氧化还原性质研究

用直接法合成了以锰为中心原子的过渡元素和钨的三元杂多配合物,经ICP和TG曲线确定其化学式为K5,6[MnM(OH2)W11O39]·xH2O(M=Mn2+,Fe3+,Co2+,Ni2+,Cu2+,Zn2+和Cd2+),采用IR,UV,XRD和XPS等手段对配合物结构进行了表征,用循环伏安测定了其系列配合物的氧化还原性质,得出系列配合物的氧化性顺序,同时讨论配合物的热稳定性.     

聚合物与表面活性剂相互作用的分子模拟研究进展

聚合物与表面活性剂复配体系已广泛应用于医药、生物、石油石化等领域。从微观上认识其相互作用机理对指导其生产实际有着重要作用,因而此方面的研究倍受关注。随着分子模拟技术的发展,聚合物与表面活性剂在分子水平上的相互作用机理研究已经被广泛开展,并获得了大量有用的信息。本文综述了耗散粒子动力学(DPD)和粗粒度分子动力学(CG-MD)在聚合物与表面活性剂相互作用方面的应用,分别对中性聚合物与离子型表面活性剂,以及带相反电荷的聚电解质和表面活性剂在溶液相和界面相的相互作用进行了阐述,并揭示了聚合物/表面活性剂聚集体结构形态的变化规律。     

Theoretical study on polynuclear superalkali cations with various functional groups as the central core

A new series of polynuclear superalkali cations YLi(3)(+) (Y = CO(3), SO(3), SO(4), O(4), and O(5)) has been created when the central group is surrounded by alkali atoms. The structural characteristics and stabilities of these systems are provided on the basis of ab initio methods. In the lowest-energy structure of the CO(3)Li(3)(+), SO(3)Li(3)(+), and SO(4)Li(3)(+) cations, the central Y (Y = CO(3), SO(3), and SO(4)) group features a slight distortion. The global minima of O(4)Li(3)(+) and O(5)Li(3)(+) are of the forms O(2)(-)(Li(+))(3)O(2)(-) and O(2)(-)(Li(+))(3)O(3)(-), respectively, both of which contain two monovalent ion units. The structural integrity of the central Y group and the arrangement of the lithium ligands are two influencing factors on the vertical electron affinities (EA(vert)) for the YLi(3)(+) species. The YLi(3)(+) cation, with its lithium ligands being distributed evenly or far from each other, tends to exhibit a low EA(vert) value, whereas a greater extent of cleavage of the central Y group leads to a higher EA(vert) value and even makes some species lose their superalkali nature.     

Synthesis and Characterization of Surface-Active Ionic Liquids Used in the Disruption of Escherichia Coli Cells

Twelve surface-active ionic liquids (SAILs) and surface-active derivatives, based on imidazolium, ammonium, and phosphonium cations and containing one, or more, long alkyl chains in the cation and/or the anion, were synthetized and characterized. The aggregation behavior of these SAILs in water, as well as their adsorption at solution/air interface, were studied by assessing surface tension and conductivity. The CMC values obtained (0.03–6.0 mM) show a high propensity of these compounds to self-aggregate in aqueous media. Their thermal properties were also characterized, namely the melting point and decomposition temperature by using DSC and TGA, respectively. Furthermore, the toxicity of these SAILs was evaluated using the marine bacteria Aliivibrio fischeri (Gram-negative). According to the EC₅₀ values obtained (0.3–2.7 mg L⁻¹), the surface-active compounds tested should be considered “toxic” or “highly toxic”. Their ability to induce cell disruption of Escherichia coli cells (also Gram-negative), releasing the intracellular green fluorescent protein (GFP) produced, was investigated. The results clearly evidence the capability of these SAILs to act as cell disruption agents.