Automatic spectrolfluorimetric method for the determination of dysprosium as its ternary complex with EDTA and Tiron

The automatic method is based on the ternary complex formed with EDTA and Tiron. The method is satisfactory or quantifying 0.1–1.2 μg ml^?1 dysprosium under conditions similar to those used for terbium. The effect of other lanthanides, yttrium, thorium, and dioxouranium(VI) on the fluorescence intensity is described; the main interference is from terbium(III).     

Study on line tension of air/hexadecane/aqueous surfactant system

We measured the line tension of the air/hexadecane/aqueous solution of the dodecyltrimethylammonium bromide (DTAB) system as a function of the molality of DTAB aqueous solution at 298.15 K. The experimental values of the line tension were 10^?10 to 10^?12 N, and they coincided with the theoretical estimates. Furthermore, it was found that the line tension changes in sign from positive to negative at around 0.750 mmol kg^?1. This concentration is close to the point of transition from partial to frustrated-complete wetting. Taking into account the profiles of the free energy of the air/water surface, previously developed by Indekeu to understand the interrelationship between the wetting transition and line tension, it is suggested that the sign reversal of the line tension can be attributed to the transition from partial to frustrated-complete wetting.     

表面活性剂对金属荧光反应的增敏作用

研究了各种类型的表面活性剂对铪-栎精、锆-栎精、锡-桑色素、镁-8-羟基喹啉-5-磺酸(镁-H_QS)、锌-H_2QS、镉-H_2QS、铽-EDTA-磺基水杨酸体系荧光光谱的影响.结果表明:在适当的表面活性剂存在下,各种配合物的荧光强度均大大增强.确定了在有表面活性剂参与下三元配合物的最佳形成条件;以荧光法测定了这些荧光配合物的组成.用相对法测定了有表面活性剂和没有表面活性剂存在时荧光配合物的量子效率,并计算了在激发波长下各自的摩尔吸光系数.发现在有表面活性剂存在时,由于生成了有固定组成的三元离子缔合物,荧光配合物的量子效率和摩尔吸光系数都有不同程度的提高,从而大大增强了它们的荧光强度.讨论了表面活性剂胶束的作用以及表面活性剂的分子结构对荧光反应的影响.指出只有那些分子中带电荷基团与共轭大π键不相邻的表面活性剂才能对荧光反应起增敏作用.利用表面活性剂的增敏作用有可能建立一些高灵敏度的金属荧光分析法.     

Effects of surfactant/water ratio and dye amount on the fluorescent silica nanoparticles

Effects of surfactant/water volume ratios and dye amounts on the properties of micelles and fluorescence silica nanoparticles were studied in microemulsions containing nonionic surfactant Triton X-100, hexanol as co-surfactant, cyclohexane as organic solvent, and metal organic dye (tris(2,2′-bipyridyl)dichlororuthenium) via fluorescence probe technique, TEM, and XPS. Fluorescence probe measurements show that the micelle microenvironment becomes stable at the surfactant/water volume ratio higher than 3.5 and the incubation time longer than 10 h. The data suggest that the silica shell, which is formed at the surfactant/water ratio of 3.5, yields an efficient protection of dye molecules against the e-beam irradiation and result in high photostability of fluorescent silica. We pioneered the localization of dye molecules on the surface of dye-doped silica and found that an increase of dye amounts, beyond a threshold, in the microemulsion cannot enhance the fluorescence intensity of dye-doped nanoparticles. These results are of significant importance for optimizing the synthesis of fluorescent nanoparticles with high photostability and low cost.     

Sensitization of surfactant on the fluorescent reactions of metals

The effects of different surfactants on the Hf-quercetin, Zr-quercetin, Sn-morin, Mg-oxine-5-sulfonic acid (H₂QS), Zn-H₂QS, Cd-H₂QS and Tb-EDTA-sulfosalicylic acid (SSA) systems were investigated. It was found that the fluorescence intensity of each complex studied is greatly increased in the presence of a suitable surfactant. The optimum conditions for the formation of the ternary complexes involving a surfactant were found, and the compositions of these ternary complexes were established by fluorometry. In the presence or absence of a surfactant, the quantum efficiencies (ϕ) of fluorescent complexes were measured by the relative method, and their molar absorptivities at the excitation wavelength (ϵ_ex) were calculated. It was found that the quantum efficiencies and molar absorptivities of fluorescent complexes were increased to various degrees because of the formation of the ionic associated complexes with fixed compositions, thus leading to greatly increased fluorescence intensity. The function of surfactant micelles and the relation between the molecular structures of surfactants and their effects on the fluorescent reactions were discussed. It is noted that only those surfactants with their aromatic system uncharged or unconnected directly with a charged functional group can sensitize the fluorescent reactions. By making use of the surfactant sensitization it is possible to develop some highly sensitive fluorometries of the metals.     

Chitosan/anionic surfactant complex membranes for the pervaporation separation of methanol/MTBE and characterization of the polymer/surfactant system

For the separation of methanol/MTBE (methyl tert-butyl ether) mixtures, methanol selective chitosan composite membranes were prepared and tested for pervaporation experiments. When anionic surfactants are added into the cationic chitosan solution, the solution viscosity was drastically decreased due to the collapsed chain conformation. Pervaporation characteristics of surfactant modified chitosan membrane were substantially improved due to the decreased membrane thickness and possible enhanced affinity to methanol. Rheological data of the casting solution was measured using viscometer and the surface morphology of the surfactant complexed chitosan membrane was investigated by atomic force microscopy (AFM).     

Study on the supramolecular multirecognition mechanism of beta-naphthol/beta-cyclodextrin/anionic surfactant in a tolnaftate hydrolysis system

Based on the fact that tolnaftate degrade to beta-naphthol sodium (RONa) at 5.00 mol/L NaOH solution and RO(-) was protonated to ROH after being acidified and adjusted to the pH 4.50 by acetic acid-sodium acetate buffer solution, we studied and discussed the mechanism of the supramolecular multirecognition interaction among the anionic surfactants sodium lauryl sulfate (SLS), beta-cyclodextrin (beta-CD), and beta-naphthol (ROH) by means of fluorescence spectrum, surface tension of the solution, infrared spectrograms, and (1)HNMR spectroscopy. The apparent formation constant of the ternary inclusion complex was determined to be (5.48 +/- 0.13) x 10(3) L(2)/mol(2). The thermodynamic parameters (DeltaG degrees, DeltaH degrees, DeltaS degrees ) for the formation of the inclusion complexes were obtained from the van't Hoff equation. It was indicated that the multiple and synergistic protection effect of SLS and beta-CD on the excited singlet state ROH played very important roles in the enhancement of the fluorescence of ROH. Results showed that, at room temperature, the naphthalene ring of ROH and the hydrophobic hydrocarbon chain of SLS were included into the cavity of beta-CD to form a ROH/SLS/beta-CD ternary inclusion complex with stoichiometry of 1:1:1, which provided effective protection for the excited state of ROH and increased the fluorescent intensity of ROH obviously.     

A robust combination of dysprosium vanadate/halloysite nanotubes: the electrochemical system for dimetridazole detection

Dimetridazole (DMD) is one of the significant antibiotic drugs of nitroimidazoles derivates that have attracted increasing attention in the medical field due to its pharmacological and toxicological activity. The development of high-performance sensors for continuous monitoring of DMD in food and environments is receiving increasing attention. Herein, an electrochemical platform was designed based on a dysprosium vanadate/halloysite nanotubes (DyV/HNTs) nanocomposite for the detection of DMD. The DyV/HNTs nanocomposite was examined by various spectroscopic and analytical techniques. The DyV/HNTs based electrochemical sensor reveals a distinctly higher electrocatalytic response to the reduction of DMD due to the good physiochemical properties compared to other electrodes. The DyV/HNTs based electrochemical sensor for DMD covered two linear ranges of 0.001–0.54 and 0.54–188 μM with a detection limit of 0.9 nm through the amperometric method, which is better than those previously reported. Furthermore, selectivity, stability, repeatability, and reproducibility studies were performed. Moreover, the fabricated DyV/HNTs sensor was successfully applied for the reliable discrimination of DMD in biological and water samples with satisfactory recovery values. The results indicated that this DyV/HNTs nanocomposite may be a promising electrochemical sensing platform for the determination of DMD.     

液流电池正极活性物质钛铁试剂初探

应用循环伏安法研究钛铁试剂(4,5-二羟基-1,3-苯二磺酸钠)电对(石墨基底)在水溶液中的电化学行为.实验表明,溶液pH<4时,该试剂的氧化还原反应电位较高,可逆性好.以其作正极与V(III)/V(II)负极组成液流电池,在硫酸介质中,充放电库仑效率可达90%以上,而且循环寿命较好,性能衰减小,具备作为液流电池正极活性物质的可行性.     

CDG/表面活性剂二元体系性能研究

针对温度70℃、矿化度20794mg/L的油藏,开展了胶态分散凝胶(CDG)/表面活性剂二元体系研究。研究了超支化聚合物浓度、聚交比对新型CDG成胶性能影响,结果表明聚合物浓度为800mg/L、聚交比为20∶1的CDG体系具有较好的成胶性能;扫描电镜实验表明CDG呈胶态分散结构;TGU装置测定CDG的转变压力,聚合物浓度为800mg/L、聚交比为20∶1体系成胶后形成CDG转变压力为52.4KPa。将CDG与表面活性剂SA复配后形成CDG/表面活性剂二元体系,与CDG相比其粘度增大、界面张力降低。岩心驱油实验表明:超支化聚合物浓度为800mg/L CDG与0.2%表面活性剂复配的二元体系的提高采收率程度比CDG提高采收率程度高6.58%。     

Surface and fluorescence properties of a novel fluorescent surfactant

A novel kind of fluorescent surfactant having 7-hydroxylcoumarin group in the long alkyl chain was synthesized. The critical micelle concentration (CMC), surface tension (γ_cmc) at CMC and absorption, fluorescence properties of this product were determined. From the variations of fluorescence spectra in different solvents, it is observed that the polarity and dielectric constant of the solvents play important roles in the maximum fluorescence intensity and wavelength. Moreover, the surprised exhibition of two fluorescence bands in neutral and alkaline solutions has been attributed to the superexciplex formation of the product molecules. Also, the lower product concentration measuring the fluorescence properties as well as the supposed configuration of hydrogen bond of the product indicate that the larger aggregations cannot exist in alkaline solutions. The superexciplex is a possibility with two or more polar excited molecules together to form an excited state association.     

NMR study of polymer surfactant interaction in the system HPMC/SDS/water

The interaction between the nonionic water soluble polysaccharide hydroxypropylmethyl cellulose (HPMC) and the low molecular weight amphiphile sodiumdodecyl sulphate (SDS) has been studied by NMR¹H-chemical shift measurements and by self-diffusion NMR measurements. The polymer concentration has been kept sufficiently dilute to avoid coil overlap and the SDS composition range goes from zero up to well above the normal CMC point. Although a different fraction was used, the present results agree well with previous results for the same system obtained by techniques other than NMR and show very clear break points that can be related to the polymer surfactant interaction. Furthermore, it can be inferred from the chemical shift measurements that the structure of the micellar clusters are similar whether polymer is present or not. From a combination of chemical shift and self diffusion measurements it is also found that neither the size nor the shape of the clusters seem to change significantly in the composition interval investigated.     

Adsorption and elektrokinetic properties of the system: carboxymethylcellulose/manganese oxide/surfactant

The adsorption of carboxymethylcellulose (CMC) in the presence of the surfactants: anionic SDS, nonionic polyethylene glycol p-(1,1,3,3-tetramethylbutyl)-phenyl ether (Triton X-100) and their mixtures SDS/polyethylene glycol p-(1,1,3,3-tetramethylbutyl)-phenyl ether with different molar ratios (1:1; 1:3 and 3:1) from the electrolyte solutions (NaCl, CaCl₂) on the manganese dioxide surface (MnO₂) was studied. In every measured system the increase of CMC adsorption in the presence of surfactants was observed. This increase was the smallest in the presence of SDS, a bit larger in the presence of polyethylene glycol p-(1,1,3,3-tetramethylbutyl)-phenyl ether and the largest when the mixtures of SDS/polyethylene glycol p-(1,1,3,3-tetramethylbutyl)-phenyl ether were used. Among the measured mixtures, the mixture of SDS/polyethylene glycol p-(1,1,3,3-tetramethylbutyl)-phenyl ether with the molar ratio 1:3 caused the largest increase of CMC adsorption amount. These results are a consequence of formation of complexes between the carboxymethylcellulose macromolecules and the surfactant molecules. In order to determine the electrokinetic properties of the system the surface charge density of MnO₂ and the zeta potential measurements were conducted in the presence of the CMC macromolecules and the surfactants. The obtained data showed that the adsorption of CMC or CMC/surfactants complexes on the manganese dioxide surface strongly influences the structure of the electric double layer MnO₂/electrolyte solution.     

Effect of surfactant structure on the residual fluorescence of micelle-based fluorescent probes

In the present paper we have investigated some photo-physical characteristics of different micellar-based fluorescent probes containing a fluorophore (pyrene) and a quencher unit (dodecyl-dioxo 2,3,2). The fluorescent response of the probe in the presence of Cu(II) ions was studied using different micellar substrates, and it was found that the pH at which the On-Off jump occurs is not influenced by the chemical structure of surfactant. In addition, the experimental residual fluorescence is not proportionally affected by microviscosity or by the size of the micellar aggregates. The signal of the native fluorescence of pyrene was observed even when the quencher's occupancy number was greater than one. Moreover, we observed discrepancies between experimental values and calculated residual fluorescence using Laplace data. These results were interpreted suggesting that the residual fluorescence has two main components, one that seems to be independent on micellar properties, while the other is directly related to location of molecules inside the surfactant aggregates that serve as substrate.     

Conductometric study of the complex system polyelectrolyte/surfactant in aqueous solution

In this work, the interaction between the anionic surfactant sodium dodecyl sulfate (SDS) and the polyelectrolyte complex hydrolyzed polyacrylamide/poly(4-vinylpyridine) (AD37–P4VP) in aqueous solution was investigated by conductometric measurements. Three main series with SDS concentrations of 0.01, 0.25 and 1 % and in a wide range of P4VP and AD37 concentrations, from 0.1 × 10^?4 to 4 × 10^?4 g/ml, and from 10^?4 to 10^?3 g/ml, respectively, were studied. The polyelectrolyte complex interacts strongly with the SDS surfactant. These interactions are of electrostatic and hydrophobic types. Thus, the effect of salt on the critical micelle concentration of SDS, and the neutralization degree on behavior conductivity of the mixture, were quantified.     

混合表面活性剂双水相性质的研究

本文利用电导法及冷冻蚀刻实验技术研究了正负离子表面活性双水相上相中的液晶结构状态及其相关性质。在双水相相体积比一组成关系曲线上及上相电导率—组成曲线上,均存在明显的转折。转折处组成是有偏光现象的双水相与无偏光现象的双水相的分水岭,立方液晶导电能力与容纳水的能力强于层状液晶或六方液晶。冷冻蚀刻实验证实了无偏光现象的立方液晶的存在。本文对一些机理进行了讨论。     

表面活性剂体系萃取分离贵金属离子的研究

研究了在TritonX 100 (NH4)2SO4 络合剂体系中,贵金属离子的萃取分离行为。考察了金属络合物的液 液两相间的分配行为及影响络合物萃取行为的各种因素,优化了萃取分离条件。实验结果表明,在pH7.0～7.5的溶液中,络合剂PAR能与Pd(Ⅱ)形成稳定的络合物,可被定量萃取,实现了Pd(Ⅱ)与Pt(Ⅵ)、Ir(Ⅵ)、Mo(Ⅵ)等混合离子间的定量分离。混合离子分离中,Pd(Ⅱ)的回收率为97.5%～100.8%。     

Characterization of fluorescent surfactant aggregates by fluorimetric and viscosimetric techniques

Summary A combination of fluorimetric and viscosimetric methods was used to characterize N,N-dimethyl-N-2-(4-(t-butylphenoxy)ethoxy)ethyl-N-hexadecylammonium chloride (BDHC), a doubletailed surfactant with dissimilar tail groups.BDHC was observed to fluoresce at 315 nm when excited at 274 nm, a feature which could be utilized to determine its critical micelle concentration (CMC). A value of 3.98×10^–5 M was obtained and was observed to be slightly temperature dependent with aT _min of 25.35°C. Fluorescence quenching experiments using 4-nitroaniline as a quencher were performed in order to determine the aggregation number which was found to be 42.0. The hydrodynamic radius of 21.91 Å was obtained using data from viscosimetric experiments. These data, together with theTanford andEinstein-Stokes relationships, were used to determine the micellar structure (spherical) and the diffusion coefficient (D=0.97×10^–6 cm²/s), respectively. The G of micellization forBDHC was determined to be –34.9 kJ/mol.

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Charakterisierung fluoreszierender oberflächenaktiver Aggregate mittels Fluorimetrie und Viskosimetrie

Zusammenfassung Die Verbindung N,N-Dimethyl-N-2-(4-(t-butylphenoxy)ethoxy)ethyl-N-hexadecylammoniumchlorid (BDHC), eine oberflächenaktive Substanz mit zwei unterschiedlichen Seitenketten, wurde mittels einer Kombination von fluorimetrischen und viskosimetrischen Methoden charakterisiert. Anregung bei 274 nm ruft eine Fluoreszenz bei 315 nm hervor; diese Eigenschaft wurde zur Bestimmung der kritischen Micellenkonzentration (CMC) herangezogen. Es wurde ein geringfügig temperaturabhängiger Wert von 3.98×10^–5 M gefunden (T _min=25.35°C). Quenchexperimente mit 4-Nitroanilin ergaben eine Aggregationszahl von 42.0, viskosimetrische Untersuchungen einen hydrodynamischen Radius von 21.91 Å. Die erhaltenen Daten erlauben zusammen mit den Beziehungen nachTanford undEinstein-Stokes die Bestimmung der Micellenstruktur (sphärisch) und des Diffusionskoeffizienten (0.97×10^–6 cm²/s). Das G der Micellenbildung fürBDHC beträgt –34.9 kJ/mol.

     

Microfluidic exploration of the phase diagram of a surfactant/water binary system

We investigate the behavior of a binary surfactant solution (AOT/water) as it is progressively concentrated in microfluidic evaporators. We observe in time a succession of phase transitions from a dilute solution up to a dense state, which eventually grows and invades the microchannels. Analyzing these observations, we show that, with a few experiments and a limited amount of material, our microdevices permit a semiquantitative screening of the equilibrium phase diagram as well as a few kinetic observations.