The research presented in this paper investigates the adsorption of cation surfactantsscetyltrimethylammonium bromide (CTAB) and cetylpyridinium chloride (CPC)sonto magnetic nanoparticles and the application of this mixed hemimicelles solidphase extraction (SPE) method for the preconcentration of several typical phenolic compoundssbisphenol A (BPA), 4-tertoctylphenol (4-OP), and 4-n-nonylphenol (4-NP)sfrom environmental water samples. In this novel SPE method, the charged surfactants CTAB and CPC form mixed hemimicelles on Fe 3 O 4 nanoparticles (Fe 3 O 4 NPs), which causes retention of analytes by strong hydrophobic and electrostatic interactions. The SPE method combines the advantages of mixed hemimicelles and magnetic nanoparticles. In order to provide guidelines for the mixed hemimicelles SPE method development, surfactant adsorption isotherms and -potential isotherms were also investigated. The main factors affecting the adsolubilization of analytes, such as the amount of Fe 3 O 4 NPs and surfactants, the type of surfactants, the solution pH, the sample loading volume, and the desorption conditions, were investigated and optimized. A concentration factor of 800 was achieved by the extraction of 800 mL of several environmental water samples using this SPE method. Under the selected conditions, detection limits obtained for BPA, 4-OP, and 4-NP were 12, 29, 34 ng/L, respectively. The accuracy of the method was evaluated by recovery measurements on spiked samples, and good recoveries (68-104%) with low relative standard deviations from 2 to 7% were achieved. The advantages of this new SPE method include high extraction yields, high breakthrough volumes, short analysis times, and easy preparation of sorbents. To the best of our knowledge, this is the first time that a mixed hemimicelles SPE method based on magnetic separation and nanoparticles has been used for the pretreatment of environmental water samples.
By an undirected rigid formation of mobile autonomous agents is meant a formation based on graph rigidity in which each pair of "neighboring" agents is responsible for maintaining a prescribed target distance between them. In a recent paper a systematic method was proposed for devising gradient control laws for asymptotically stabilizing a large class of rigid, undirected formations in two-dimensional space assuming all agents are described by kinematic point models. The aim of this paper is to explain what happens to such formations if neighboring agents have slightly different understandings of what the desired distance between them is supposed to be or equivalently if neighboring agents have differing estimates of what the actual distance between them is. In either case, what one would expect would be a gradual distortion of the formation from its target shape as discrepancies in desired or sensed distances increase. While this is observed for the gradient laws in question, something else quite unexpected happens at the same time. It is shown that for any rigidity-based, undirected formation of this type which is comprised of three or more agents, that if some neighboring agents have slightly different understandings of what the desired distances between them are suppose to be, then almost for certain, the trajectory of the resulting distorted but rigid formation will converge exponentially fast to a closed circular orbit in two-dimensional space which is traversed periodically at a constant angular speed.
Mixed hemimicelles solid-phase extraction (SPE) based on cetyltrimethylammonium bromide (CTAB)-coated nano-magnets Fe 3 O 4 was investigated for the preconcentration of four chlorophenols (CPs) in environmental water samples prior to HPLC-spectrophotometry determination in this paper. By the rapid isolating (about 5 min) of Fe 3 O 4 nanoparticles (NPs) through placing a Nd-Fe-B strong magnet on the bottom of beaker, the time-consuming preconcentration process of loading large volume sample in conversional SPE method with a column can be avoided. The unique properties of Fe 3 O 4 NPs such as high surface area and strong magnetism were utilized adequately in the SPE process. This novel separation method produced a high preconcentration rate and factor. A comprehensive study of the adsorption conditions such as the Fe 3 O 4 NPs zeta-potential, CTAB added amounts, pH value, standing time and maximal extraction volume was also presented. Under optimized conditions, four analytes of 2-chlorophenol (2-CP), 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (TCP) and pentachlorophenol (PCP) were quantitatively extracted. The method was then used to determine four CPs in five real environmental water samples. High concentration factors (700) were achieved for each of the analytes, with observed detection limits ranging between 0.11 and 0.15 g L −1 . The accuracy of method was evaluated by recovery measurements on spiked samples. Good recovery results (83-98%) with satisfactory relative standard deviation (RSD) were achieved. It is important to note that satisfactory preconcentration factors and extraction recoveries for the four CPs were obtained with only a little amount of Fe 3 O 4 NPs (0.1 g) and CTAB (60 mg). To the best of our knowledge, this was the first time a mixed hemimicelles SPE method based on Fe 3 O 4 NPs magnetic separation had been used for the pretreatment of environmental water samples.
Ionic liquid mixed hemimicelles-based solid-phase extraction for the preconcentration of five phthalates in environmental water sample was investigated in this paper. A comparative study on the use of room temperature ionic liquids (RTILs) 1-hexyl-3-methylimidazolium bromide ([C 6 mim]Br) and 1-dodecyl-3-methylimidazolium bromide ([C 12 mim]Br)-coated silica as sorbents was presented. Owing to having bigger adsorption amounts for analytes [C 12 mim], Br-coated silica was selected as SPE material and the five analytes di-ethyl-phthalate (DEP), di-n-propyl-phthalate (DnPP), di-n-butyl-phthalate (DnBP), di-cyclohexyl-phthalate (DcHP) and di-(2-ethylhexyl)-phthalate (DEHP) can be quantitatively extracted under optimal conditions. The analytes retained on the cartridge were desorbed completely with 3 mL methanol (pH 2). Predominant factors influencing the extraction efficiency, such as RTILs concentration, pH value, ionic strength and breakthrough volume were discussed. The proposed method had been applied to determining the five phthalates in four environmental water samples and concentration factor of 600 was achieved easily. Detection limits obtained ranged between 0.12 and 0.17 g/L. The accuracy of this method was evaluated by recovery measurement on spiked samples, and good recovery results (85-107%) with relative standard deviation (R.S.D.) of below 6% were achieved.
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