Oxide Units Research Articles

Degradation of the nonionic surfactant Triton™ X-45 with HO[rad] and [formula omitted] – Based advanced oxidation processes

In the present study the nonionic surfactant Triton™ X-45 (TX-45), an octylphenol polyethoxylate, was treated by persulfate (S2O82-)/UV-C process involving the intermediacy of sulfate radicals and the relatively well-known hydrogen peroxide (H2O2)/UV-C process. TX-45 removal occurred rapidly via both advanced oxidation processes. Complete oxidation was also achieved under the studied reaction conditions, however required extended treatment periods (>30min) and high oxidant concentrations (⩾2.5mM). Several degradation products could be qualified via GC–MS and HPLC analyses. Inspection of the identified degradation products indicated that the reaction mechanism of TX-45 was a combination of various pathways; (i) progressive shortening of the exhoxylate chain leading to relatively short-chain TX-45 and ultimately octylphenol, (ii) ω-carboxylation of the terminal alcoholic groups yielding octylphenol ethoxy carboxylates (OPECs) and (iii) central fission of the ethoxy chain resulting in the formation of polyethylene glycols (PEGs). Continued oxidation of the primary degradation products resulted in mono- and di-carboxylated PEGs. Degradation products bearing a smaller number of ethylene oxide units (⩽3) were generated during H2O2/UV-C treatment, whereas OPECs was only detected during S2O82-/UV-C treatment of TX-45. Acetic and succinic acids were quantitatively identified during S2O82-/UV-C treatment, whereas oxalic and fumaric acids were additionaly detected during H2O2/UV-C oxidation. Product identification suggested similar reaction pathways for the treatment of TX-45 by SO4-- and HO-driven oxidation processes.

Surface Active and Thermodynamic Properties in Relation to the Demulsification Efficiency for Some Ethoxylated Derivatives of Alkyldiamines and Polyalkylenepolyamines

In this work, nine monostearic esters of ethoxylated dialkyle-amine (group I) and ethoxylated polyalkylenepolyamine (group II) nonionic surfactants were prepared and characterized by FTIR spectroscopy and nitrogen content. The 1,4-diaminobutane (DAB), 1,6 diamino hexane (DAH), 1,8-diamino-octane (DAO), diethylenetriamine (DETA), triethylenetetramine (TETA), and tetraethylenepentamine (TEPA) were ethoxylated at 50, 100, 150 ethylene oxide units individually. The ethoxylated products of (group I) reacted with stearic acid to give the monostearate products. The surface tension of the prepared compounds were measured at 25°C and 60°C. The thermodynamic parameters of micellization and adsorption were also calculated. The surface active properties, such as critical micelle concentration (CMC), maximum surface excess concentration (Γmax), effectiveness of surface tension reduction (πcmc), and minimum area per molecule at the aqueous solution-air interface (Amin), have been calculated. The surface active and thermodynamic properties of the prepared compounds were correlated to their chemical structure. It was found that CMC decreases when increasing the molecular weight of polyethylene oxide units. Furthermore, the data show that the synthesized surfactants favor adsorption than micellization, so that they can be used as demulsifiers for waxy crude oil emulsion (BSW 18%). In this respect, the demulsification test was carried out and the results of demulsification efficiency were correlated to the chemical composition of the investigated compounds. Some factors that affect the demulsification efficiency were also considered such HLB, concentration and time. The maximum demulsification efficiency (100%) was obtained by DAOE150-M and TEPAE150 at 60 and 45 minutes (300 ppm), respectively.

Demulsification Efficiency of Some New Stearate Esters of Ethoxylated and Propoxylated 1,8-Diamino-Octane for Water in Crude Oil Emulsions

In this work, eight demulsifiers were prepared from 1,8-diamino-octane (DAO). The DAO was ethoxylated or propoxylated up to 100 ethylene or propylene oxide units respectively. These alkoxylated products were esterified to mono, di, tri, and tetra stearate. The chemical structure was confirmed by FTIR and nitrogen content. The surface active parameters of these surfactants were investigated on the basis of the surface tension measurements at 25°C and 60°C. These surfactants were tested as emulsion breakers (demulsifiers) against waxy crude oil emulsion (Water content (BSW) = 18%). From the obtained data, it was found that the prepared materials have surface active properties let them act as good demulsifiers. The maximum demulsification efficiency (100%) was obtained by DAOE100-1 at 400 ppm[30 min], the mixture of (DAOE100-1 + DAOP100-2) in ratio [3:1] at 400 ppm and (DAOE100-2 + DAOP100-1) in ratio [1:3] at 400 ppm at temperature 60°C the time taken for complete water separation was 15 and 9 minutes. for these mixtures, respectively. The flow properties of the emulsion with and without the demulsifier were investigated. The obtained results showed that the demulsifiers used enhance the dynamic viscosity and yield value (τB). The viscosity was reduced from 10.5 for the untreated crude oil to 3.58 for the treated crude oil at concentration 100 ppm and a temperature of 60°C, meanwhile the τB was reduced from 0.054 for crude oil to 0.013 for the treated sample at the same condition.

Chain Length Effects on the Dynamics of Poly(ethylene oxide) Confined in Graphite Oxide: A Broadband Dielectric Spectroscopy Study

The dynamics of poly(ethylene oxide) (PEO) intercalated in the subnanometer-spaced graphite oxide (GO) layers is investigated by using broadband dielectric spectroscopy (BDS). To this end, we compare BDS data obtained for PEO chains of increasing lengths, from three monomeric units to several thousand repetitive ethylene oxide units (n = 3–2135). Two relaxations were clearly identified for the confined PEO. The slowest one is proposed to originate from interfacial polarization. It is dependent on the chain length and exhibits a change in activation energy at 247 K, a temperature at which the GO exhibits an interlayer expansion when subjected to an increase in temperature. The fastest relaxation is nearly independent of the chain length, in contrast to the behavior that we found for the β-relaxation of bulk PEO. These results strengthen a previous hypothesis suggesting the emergence of a new set of chain length scales primarily dictated by the presence of anchoring points on the GO substrate upon intercala...

Fatty Acids in Heterocyclic Synthesis. Part XIV: Synthesis of Surface Active Agents from Some Novel Class of Oxadiazole, Thiadiazole and Triazole Derivatives Having Microbiological Activities

AbstractReaction of stearic acid with semicarbazide in refluxing POCl3 afforded 2‐amino‐5‐heptadecyl 1,3,4‐oxadiazole. Acylation of the amino group with acetic anhydride, ethyl chloroacetate and chloroacetic acid gave amide and β‐amino acid derivatives. These compounds were cyclized to imidazo[2,1‐b]oxadiazole derivatives by two different techniques. Treating the starting oxadiazole compound with P2S5, hydroxyl amine and hydrazine hydrate in benzene afforded thiadiazole and triazole derivatives. Unexpectedly, triazolo[3,4‐b][1,3,4]oxadiazole derivative was obtained when 1,3,4‐oxadiazole derivative was refluxed with hydrazine hydrate in ethanol. The biological activities of the synthesized compounds were screened in vitro against some gram positive and gram negative bacteria and fungi. Addition of quantitative amount of propylene oxide units (3, 5, 7 mol) to the synthesized compounds afforded new nonionic surfactants. The physico‐chemical and surface properties of the novel synthesized surfactants such as surface and interfacial tension, cloud point, wetting time, emulsion stability, foam height, CMC, resistance to hydrolysis and their biodegradability were investigated. In addition, surface parameters including effectiveness (πCMC), efficiency (PC20), maximum surface excess (Γmax) and (Amin) were examined.

Synthesis and Evaluation of New Demulsifiers Incorporating Linear Alkyl Benzene Moiety for Treating Water-in-Oil Emulsion

In the present study, five types of water soluble demulsifiers based on linear alkyl benzene were prepared. The chemical structures of the prepared demulsifiers were elucidated using Fourier transform-infrared (FTIR) and 1H NMR spectra. Different factors affecting demulsification efficiency such as; water content, demulsifier concentration, hydrophilic lipophilic balance (HLB), and ethylene oxide unit were investigated. Also, the rheological properties in relation to demulsification efficiency were studied. The surface and thermodynamic parameters of the prepared demulsifiers were determined at 25°C including, surface tension (γ) and effectiveness, maximum surface excess (Γmax), and minimum surface area (Amin). From the obtained data, it was found that the demulsification efficiency increases with increasing the water content and concentration of the demulsifiers. Primarily evaluation study of demulsification performance of the new demulsifiers showed that as the ethylene oxide unit in the demulsifiers increase (10–40 ethylene oxide units), the performance of the demulsifiers increasing, however, it decrease in case of demulsifiers with (80 ethylene oxide unit).

A Novel Aminoalkylsilane Compound with Oligo(ethylene oxide) Units as Effective Additive for Improving Cyclability of Lithium-ion Batteries

A new aminoalkylsilane compound, ((2-(2-(N,N-dimethylamino)ethoxy)ethoxy) methyl)trimethylsilane (TMSC1N2) based on the oligo(ethylene oxide) chain end-capped with organosilicon functional group and alkylamine group on each end, was introduced as an electrolyte additive for lithium-ion batteries. Electrochemical performances of different volume ratios of TMSC1N2 in the baseline electrolyte were conducted through cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge/discharge tests of lithium-ion batteries. With adding 5 vol.% TMSC1N2 to the baseline electrolyte (1 mol/L LiPF 6 in ethylene carbonate and diethyl carbonate (EC:DEC = 1:1, in volume)), the capacity retention of LiFePO 4 /Li cells could be significantly improved from 74.7% to 90.8% after 130 cycles. Furthermore, TMSC1N2 showed good compatibility with graphite electrode and would not deteriorate the electrochemical performance of graphite/Li anode cells. These data suggested that TMSC1N2 could be utilized as an effective additive for lithium-ion batteries.

Determination of the Compositional Profile for Tapered Copolymers of Ethylene Oxide and 1,2-Butylene Oxide by In-situ-NMR

In this work, 1H NMR was used to examine the anionic copolymerization kinetics of ethylene oxide and 1,2-butylene oxide. The in situ NMR technique allows monitoring the concentration profiles of both monomers simultaneously. A series of polymerization experiments at different monomer and initiator concentrations were done in order to determine the copolymerization rate constants. The data were evaluated by fitting the result of a numerical solution of the kinetic differential equations to the NMR data. This procedure allowed calculating all four rate constants, kEE, kEB, kBE, and kBB, individually instead of the commonly determined reactivity ratios rE = kEE/kEB and rB = kBB/kBE. The monomer incorporation into the copolymer chains is dominated by the different reactivities of the monomers, whereas the nature of the chain ends is of minor importance. In the system investigated ethylene oxide is about 6.5 times more reactive than 1,2-butylene oxide. The compositional profiles of the final copolymers can be calculated from the time-resolved concentration profiles. If both monomers are present at the start of the polymerization the compositional profiles have a sigmoidal shape with one chain end containing mainly ethylene oxide and the other chain end being formed almost exclusively of butylene oxide units. However, with the knowledge of the copolymerization rate constants it is possible to realize other compositional profiles. If the reactor is first charged with ethylene oxide the addition rates of butylene oxide can be calculated in order to obtain any other arbitrarily chosen compositional profile.

Can Critical Packing Parameter Depict Probe Rotation in Block-Copolymer Reverse Micelles?

Rotational diffusion of two ionic probes, cationic rhodamine 110 (R110) and anionic fluorescein (FL), has been examined in reverse micelles formed with the triblock copolymer (EO)13-(PO)30-(EO)13 (L64), where EO and PO represent ethylene oxide and propylene oxide units, respectively, with small amounts of water in p-xylene. This study has essentially been undertaken to explore the influence of mole ratio of water to copolymer (W) as well as copolymer concentration on probe rotation. On the basis of fluorescence lifetimes and reorientation times, it has been established that both R110 and FL are located in the interfacial region of L64/water/p-xylene reverse micellar system. The average reorientation time decreases by 10-35% with an increase in W for both the probes at a given copolymer concentration. However, for a particular W, the average reorientation time increases by 10-30% as the concentration of the copolymer is enhanced. From the micellar structural parameters available in the literature, critical packing parameters have been calculated for the L64/water/p-xylene reverse micellar system, and it has been noticed that the average reorientation times of both the probes scale linearly with the critical packing parameter. In essence, the results of this study indicate that the probe mobility in the interfacial region of block copolymer reverse micelles is governed by the micellar packing.

Synthesis of aminoalkylsilanes with oligo(ethylene oxide) unit as multifunctional electrolyte additives for lithium-ion batteries

Aminoalkylsilanes with oligo(ethylene oxide) units were designed and synthesized as multifunctional electrolyte additives for lithium-ion batteries. The chemical structures were fully characterized by nuclear magnetic resonance (NMR) spectroscopy and their thermal properties, viscosities, electrochemical windows, and ionic conductivities were systematically measured. With adding one of these compounds (1 vol. %, DSC3N1) in the baseline electrolyte 1.0 M LiPF6 in EC: DEC (1:1, in volume), Li/LiCoO2 half cell tests showed an improved cyclability after 100 cycles and improved rate capability at 5C rate condition. Electrochemical impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS), and energy dispersive spectroscopic (EDS) analysis confirmed the acid scavenging function and film forming capability of DSC3N1. These results demonstrated that the multifunctional organosilicon compounds have considerable potential as additives for use in lithium-ion batteries.

Investigation of Kinetic and Rheological Properties for the Demulsification Process

Chemical demulsification process is the most widely applied method of treating water in crude oil emulsions and involves the use of chemical additives to accelerate the emulsion breaking process. Hence, five demulsifiers were prepared in two steps. In the first step, the nonyl phenol was polymerized with formaldehyde to obtain five different molecular weights polymers. In the second step, the resulting polymers were ethoxylated with 50 ethylene oxide units and propoxylated with 10 propylene oxide units, yielding (D1–D5). The demulsification efficiency of these demulsifiers was investigated. The influence of viscosity on the droplet diameter for water-in-crude oil emulsion with three different ratios; 30:70, 50:50 and 70:30 (v/v) w/o emulsions were examined. The results showed that, the viscosity of w/o emulsion was strongly augmented by increasing volume of water before reaching the inversion point. The yield point which is required to start the flow decreases with decreasing water percent. The coalescence rate increases with increasing drop size for D5 as a representative sample. Results show that, the droplet size increases with increasing water content. The efficiency of water separation increases as the molecular weight increase.

Electrochemical properties of semi-interpenetrating polymer network solid polymer electrolytes based on multi-armed oligo(ethyleneoxy) phosphate

In this work we synthesize a series of plasticizers and a crosslinker based on a multi-armed oligo(ethyleneoxy) phosphate and carry out in-situ radical polymerization of the precursor solution containing the plasticizers and crosslinker to produce semi-interpenetrating polymer network (semi-IPN) solid polymer electrolytes (SPEs). A high-quality free-standing film is obtained with a tensile strength as high as 1.2 MPa. Several factors are investigated to optimize the ionic conductivity of the solid polymer electrolytes such as the length of ethylene oxide units in the plasticizers, the concentration of lithium salts, the content of the plasticizers, and the different types of lithium salts. The maximum ionic conductivity of the SPEs is found to reach 5.0 × 10−4 S cm−1 at 30 °C, together with the wide electrochemical stability window of above 5.0 V and the columbic efficiency more than 70% in reversible lithium plating–stripping cycles, making phosphate-based semi-IPN SPEs a promising candidate for application in solid-state lithium secondary batteries.

Ion transport behavior in polymerized imidazolium ionic liquids incorporating flexible pendant groups

A series of polyvinylimidazolium cations containing an ethyl, mono, or triethylene oxide pendant groups with [TFSI]− anion as counterion were synthesized via radical polymerization. The physical properties and ion conduction behaviors of the polymerized ionic liquids (PILs) were investigated to elucidate the effects of ethylene oxide unit. As the length of the ethylene oxide pendant group in the PILs increased, the glass transition temperature of PIL decreased and the ionic conductivity increased, implying that the introduction of ethylene oxide pendant group on the imidazolium cation improved the chain mobility of the resulting polymer macromolecules. When an equimolar amount of LiTFSI to the ionic groups in the PIL was added, the ionic conductivities were further enhanced up to 3×10−5Scm−1 at room temperature.

Liquid crystalline and ion-conducting properties of mesogenic dendron–coil-dendron copolymers: characterization of LC phases using normalized conductivity

We synthesized three dendron–coil-dendron block copolymers consisting of ionophilic poly(ethylene oxide) (PEO) coils and mesogenic dendrons with four octadecyl peripheries via stepwise click reactions. The obtained polymers were doped with lithium triflate, whose concentration per ethylene oxide unit was 0.05. As characterized by optical polarized microscopy (POM) and X-ray scattering techniques, polymer 1 with the shortest PEO coil (Mn = 2000 g mol−1) did not show the liquid crystalline (LC) phase, while its ionic sample (1-Li+) exhibited a hexagonal columnar LC phase. On the other hand, 2 and 3 (with PEOs of Mn = 4000 and 8000 g mol−1, respectively) displayed identical LC morphologies to 2-Li+ and 3-Li+, respectively, although the phase transition temperatures increased upon salt doping. For 2 and 2-Li+, gyroid and lamellar LC phases were observed with increasing temperature, while 3 and 3-Li+ showed only a lamellar LC phase. The observed ion-transporting behavior was strongly dependent upon the connectivity of ion-conducting domain structures. The investigation of the morphology–conductivity correlation using a normalized conductivity (σ* = σ/f, where σ and f are the original conductivity and the PEO volume fraction) indicated that the 3-D gyroid LC phase showed the highest value, while the lowest conductivity was found in the 1-D columnar structure at identical temperatures. Additionally, the gyroid to lamellar phase transition temperature of 2-Li+ could be determined by the σ*, which was consistent with the X-ray data. Consequently, the results can be explained by the fact that the ionic pathway becomes complicated when going from higher to lower dimensional structures in polygrain samples.

Ethoxylated fatty amines as corrosion inhibitors for carbon steel in hydrochloric acid solutions

The effect of three compounds of non ionic surfactants, namely, ethoxylated fatty amines with different number of ethylene oxide unit on the corrosion of carbon steel (Type L52) in 1 M HCl has been studied using weight loss and galvanostatic polarization measurements. The percentage inhibition efficiency was found to increase with increasing concentration of inhibitor, number of ethylene oxide units and with decreasing temperature. The inhibitive effect of these compounds was interpreted in view of their adsorption on the steel surface, through their ethoxy groups. The adsorption of these compounds was found to obey the Langmuir isotherm. The effect of temperature on the rate of corrosion in the absence and presence of these compounds was also studied. Some activated thermodynamic parameters were calculated.

A dopamine sensor based on a methoxypolyethylene glycol polymer covalently modified glassy carbon electrode

A dopamine (DA) sensor based on a methoxypolyethylene glycol (MPEG) polymer covalently modified glass carbon electrode (GCE) was fabricated by an electroadsorption method. The electrochemical behavior of the sensor towards the catalytic oxidation of DA in pH 5.0 phosphate buffer solution (PBS) was investigated by cyclic voltammetry. The modified electrode obviously enhanced the current response and decreased the overpotentials for the oxidation of DA. Using differential pulse voltammetry, the sensor gave a linear response to DA over the concentration range of 2.0-140 μM with a detection limit (S/N = 3) of 4.68 × 10(-8) M. It was found that MPEG can complex DA through hydrogen bonding interaction between ethylene oxide units of the polymer and the protonated dopamine in acidic PBS and preconcentrate it in the film, which improved the detection limit and sensitivity of DA. The DA sensor exhibits good sensitivity, selectivity and stability, and has been applied for the determination of DA in dopamine hydrochloride injection solution.

자기-도핑형 poly(PEGMA-co-BF3LiMA) 전해질의 합성과 이온전도도에 대한 PEGMA분자량의 영향

분자량이 각각 300(PEGMA300) 및 1100(PEGMA1100) g <TEX>$mol^{-1}$</TEX>인 PEGMA와 합성된 <TEX>$BF_3LiMA$</TEX> 리튬염을 이용하여 다양한 조성의 고분자전해질을 제조하고 전기화학적 특성을 평가하였다. 흥미롭게도 AC-impedance 측정법에 의한 상온 이온전도도는 분자량 <TEX>$300g\;mol^{-1}$</TEX>로 합성된 액체 고분자전해질에서 <TEX>$8.54{\times}10^{-7}S\;cm^{-1}$</TEX>의 값이 얻어진 반면, PEGMA1100으로 합성된 고체상태의 고분자전해질에서 최대 14배 이상 높은 <TEX>$1.22{\times}10^{-5}S\;cm^{-1}$</TEX>가 관찰되었다. 이러한 결과는 PEGMA에 ethylene oxide 단위가 5개인 <TEX>$300g\;mol^{-1}$</TEX>보다 23개인 <TEX>$1100g\;mol^{-1}$</TEX>에서 리튬이온의 배위가 쉽게 일어나기 때문으로 해석된다. 또한 양이온 수율 측정결과 리튬메탈과 <TEX>$BF_3$</TEX>간의 반응으로 인해 0.6의 비교적 낮은 값이 나왔지만 초기 3000초 동안에는 0.9 이상의 값이 관찰되어 단일이온 전도체의 특징을 보여주었다. Polymer electrolytes consisted of <TEX>$BF_3LiMA$</TEX> and 300 (PEGMA300) or 1100 (PEGMA1100) g <TEX>$mol^{-1}$</TEX> of PEGMA were prepared and the electrochemical properties were characterized. Interestingly, the AC-impedance measurement shows <TEX>$1.22{\times}10^{-5}S\;cm^{-1}$</TEX> of room temperature ionic conductivity from PEGMA1100 based solid polymer electrolytes while <TEX>$8.54{\times}10^{-7}S\;cm^{-1}$</TEX> was observed in PEGMA300 based liquid polymer electrolytes. The more suitable coordination between lithium ion and ethylene oxide (EO) unit might be the reason of higher ionic conductivity which can be possible in PEGMA1100 based electrolytes since it has 23 EO units in monomer. The lithium ion transference number was found to be 0.6 due to the side reactions between <TEX>$BF_3$</TEX> and lithium metal expecially for longer time but 0.9 was observed within 3000 seconds of measuring time which is strong evidence of a single-ion conductor.

Ammonium Y zeolite applied as a thermochemolysis reagent for identification of polyethers and polyesters

A potential thermochemolysis reagent has been tested for the pyrolysis gas chromatographic identification of polyether, polyester and polyether- or polyester-based thermoplastic polyurethane. The main advantage of ammonium Y zeolite over liquid reagents is that it does not react prior to pyrolysis, and its reactions have no incomplete products. The procedure of the thermochemolysis is as simple as running a pyrolysis-GC/MS analysis sampling a powder mixture of roughly equal mass of polymer and ammonium Y zeolite. The GC/MS chromatograms obtained show that the products of thermochemolysis are specific to the diol and dicarboxylic units of the polymer. It was observed that ethanal or 1,4-dioxane forms from ethylene oxide components of polyethers and polyesters, tetrahydrofuran from butylene oxide units, hexanedinitrile from adipate groups, and benzodinitrile from terephthalate groups.

Aggregation Behavior of Triton X-100 with a Mixture of Two Room-Temperature Ionic Liquids: Can We Identify the Mutual Penetration of Ionic Liquids in Ionic Liquid Containing Micellar Aggregates?

In this manuscript, we have characterized two different micellar aggregates containing all nonvolatile components. We have shown (i) the effect of ethylammonium nitrate (EAN) addition on the properties of micellar solution of Triton X-100 in 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF(6)) and (ii) the effect of bmimPF(6) addition on the properties of micellar solution of Triton X-100 in EAN. To investigate the effect, we have used (1)H NMR, pulsed-field gradient spin-echo NMR (PFGSE NMR), and methyl orange (MO) and coumarin 153 (C-153) as absorption and emission probes, respectively. The penetration of added EAN inside the Triton X-100/bmimPF(6) micellar aggregates is indicated by (i) red shift in both the absorption spectra of MO and emission spectra of C-153 and (ii) downfield shift of proton signals of ethylene oxide units in Triton X-100. On the other hand, (1)H NMR and PFGSE NMR indicates the penetration of added bmimPF(6) inside the Triton X-100/EAN micellar aggregates. However, the constancy of both the absorption spectra of MO and emission spectra of C-153 indicates that the microenvironment around the probe molecules remains unaffected. We have also investigated the effect of micelle formation and the effect of penetration of ionic liquids (ILs) in micellar aggregates, on the solvation dynamics of C-153. The solvent relaxation around C-153 gets retarded on going from neat ILs to the micellar solution of Triton X-100 in ILs. In addition to this, we have also observed that with the addition of EAN in Triton X-100/bmimPF(6) micellar aggregates the solvation dynamics becomes faster, whereas with the addition of bmimPF(6) in Triton X-100/EAN micellar aggregates we did not observe any notable change in solvation dynamics. This observation further supports the conclusions drawn from UV-visible and NMR studies.

Nonylphenol Polyethoxylates Degraded by Three Different Wavelengths of UV and Their Genotoxic Change—Detected by Generation of γ‐H2AX

UV rays in sunlight are an important factor in the degradation of chemicals. In this study, we investigated the degradation of nonionic surfactants, nonylphenol polyethoxylates (NPEOs) with 10 or 70 ethylene oxide (EO) units using UVA, B and C, and their genotoxic change based on phosphorylation of histone H2AX (γ-H2AX), a marker of DNA damage. NPEOs were degraded dependent on the energy of UV, that is, UVC having the highest energy was most effective, whereas UVA having the lowest energy caused little change. The EO side chain of NPEO(70) was broken near the benzene ring by UV, producing NPEOs with a shortened EO chain (around 10 units). The generation of γ-H2AX reflected the pattern of degradation; shortening of the EO chain changed NPEO(70) into an inducer for γ-H2AX, and degradation of NPEO(10) attenuated the genotoxicity. The γ-H2AX generated by NPEO(10) and UV-degraded NPEO(70) was independent of the cell cycle. The formation of DNA double strand breaks detected by gel electrophoresis was consistent with the results for γ-H2AX. These results suggested that UV rays can make NPEOs harmless or genotoxic according to the degradation of the EO side chain, the effects being dependent on wavelength.