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Modeling the Response of a Control-Released Ion-Selective Analytical Methods View Article Online PAPER View Journal | View Issue Modeling the response of a control-released ion- selective electrode and employing it for the study Cite this: Anal. Methods,2018,10, 467 of permanganate oxidation kinetics† Dean Song, ab Rongning Liang, *b Xiaohua Jiang,b Huiqing Sun,a Fanyu Kong,*a Bo Lv,a Qiannan Fanga and Wei Qinb Although polymeric membrane ion-selective electrodes (ISEs) based on outward ion fluxes have been found analytically useful, there is still a lack of a theoretical framework for this detection system. In this study, we attempted to model the response of this kind of permanganate ISE and employed this ISE to À À analyze the rapid MnO4 /H2O2 reaction. This response is attributed to H2O2 oxidation with MnO4 that is released from the inner solution to the membrane surface layer. The results show that the experimental data can be fitted well to the proposed model that is elucidated mathematically from the viewpoint of chemical kinetics. The second-order rate constant is determined at a near neutral pH and is in agreement with the acid dissociation law to provide the specific value of 370 MÀ1 sÀ1. The kinetic mechanism was then investigated by performing DFT calculations. Via analysis of the Mn–O bond length and the HOMO orbital, it has been found that the studied redox system functions similarly as the so- called hydrogen abstraction mechanism with an energy barrier of 24.5 kcal molÀ1. This study is À considered to be the first report on the simulation of MnO4 attack at the O–H bond. On the basis of Received 26th November 2017 À the transition state theory and previous studies on MnO attack at the C]C and C–H bonds, the Accepted 23rd December 2017 4 relationship between the experimental rate constant and computational energy barrier is finally DOI: 10.1039/c7ay02735d constructed. The result indicates the validity of our proposed method and makes the control-released rsc.li/methods ISE a very promising platform to study the kinetics. Introduction understanding the mechanism of potentiometric response of the ISE.9 Polymeric membrane ion-selective electrodes (ISEs) are one of To date, it has been fully realized that the transmembrane Published on 26 December 2017. Downloaded by Library of Chinese Academy Sciences 9/11/2018 3:33:27 PM. the most important analytical tools widely used for the analysis concentration gradient can cause ion ux across the polymeric of environmental and biological samples.1 They have received interface and thus deteriorate the detection limit of the ISE by signicant attention owing to the attractive features including perturbing the ion concentration at the phase boundary.10,11 high selectivity, ease of handling, and relatively low-cost.2,3 Although the ion ux cannot be entirely eliminated, this char- Recently, these well-established potentiometric sensors have acteristic of ISE has been recently found to be useful for appli- undergone a quiet revolution to reach the detection limits in the cations in polyion sensors,12 pulstrodes,13 switchtrodes,14 and sub-nanomolar levels.4,5 Inspired by this, many innovative ion-channel biosensors.15 sensing schemes have been proposed for a broad range of Recently, a novel ISE system has been exploited using targets over the last few years.6–8 Accompanied by the techno- outward ion ux (efflux) in the direction of the sample solution – logical advances, great emphasis has also been placed on under zero-current conditions.16 18 In this case, the ISE membrane can play the critical roles of both a polymer matrix for reagent release and a sensitive transducer for potentiometric a The State Agriculture Ministry Laboratory of Quality & Safety Risk Assessment for detection. Particularly, our group has developed an ionophore- Tobacco, Tobacco Research Institute, Chinese Academy of Agricultural Sciences, Qingdao 266101, China. E-mail: [email protected] free permanganate ISE that utilizes outward ion uxes through bKey Laboratory of Coastal Environmental Processes and Ecological Remediation, the membrane to provide control-released substrates for 16,19 Yantai Institute of Coastal Zone Research (YIC), Chinese Academy of Sciences (CAS), monitoring the analytes of interest. Previous studies have Shandong Provincial Key Laboratory of Coastal Zone Environmental Processes, shown that the design based on permanganate release allows YICCAS, Yantai, Shandong 264003, P. R. China. E-mail: [email protected] a sensitive and reproducible detection of reductants including † Electronic supplementary information (ESI) available: Experimental ascorbate and dopamine. However, the application of this second-order rate constants and computational energy barriers for the selected ffi permanganate oxidation reactions in water and Cartesian coordinates of the technique is still limited since all reductants that can e ciently optimized structures. See DOI: 10.1039/c7ay02735d This journal is © The Royal Society of Chemistry 2018 Anal. Methods,2018,10, 467–473 | 467 View Article Online Analytical Methods Paper react with permanganate ions may produce measured potential shown in Fig. S1 in the ESI.† For each ISE, a disk of 7 mm interference. diameter was punched from the obtained membrane and glued This is obviously disadvantageous for the analysis of to a PVC tube with a THF/PVC slurry. A 0.08 M potassium complex samples, but advantageous for the study of perman- permanganate solution containing 0.02 M NaCl was added to ganate oxidation kinetics under controllable conditions. each electrode as the inner lling solution. Before the Because the potential responses are mainly attributed to the measurements, these electrodes were activated by conditioning consumption of permanganate ion on the membrane surface them in 0.1 M NaCl for 3 days. This pretreatment was used to À layer, this permits the selective and continuous observation of make permanganate anion (MnO4 ) enter the ionophore-free the rapid permanganate oxidation process. In comparison, the ISE membrane from the inner lling solution and combine spectrophotometric method together with the stopped-ow with tridodecylmethylammonium cation (TDMAC+) via ion- À À technique would be restricted by the disturbance from the in exchange between MnO4 and Cl .Aer this step, the 20 + À situ formed colloidal manganese oxide. Consequently, it is TDMAC sites were considered to be fully saturated by MnO4 , À necessary to model the response behavior of the control- which not only could maintain the relatively stable MnO4 released permanganate ISE with respect to the chemical prin- concentration in the membrane phase but could also facilitate ciple of the reaction. the continuous ion ux from the inner lling solution to the Herein, we attempted to investigate the theoretical founda- sample solution. tion of the efflux permanganate ISE under zero-current condi- tions for the rst time and then employed this ISE as a research EMF measurements platform to study the permanganate oxidation kinetics. As Potentiometric measurements were carried out at 25 C using a proof-of-concept experiment, hydrogen peroxide (H2O2) was an LK2006 electrochemical workstation (Tianjin, China) with chosen to be the objective analyte. Note that the permanganate a saturated calomel electrode as a reference electrode in the titration has long been recognized as a reliable procedure for galvanic cell: SCE//sample solution/ISE membrane/inner lling 21 H2O2 determination. Additionally, the corresponding reaction solution/AgCl/Ag. The 20 mL sample solutions were prepared kinetics has been investigated in an acidic aqueous solution by with 0.1 M NaCl as the background electrolyte and adjusted 22 stopped- ow spectrophotometry. By the construction of with NaOH or HCl to the required pH. For each measurement, a theoretical model, the ionophore-free permanganate ISE may the ionophore-free permanganate ISE was rst taken out from have the opportunity to extend its utilization to describe the the condition solution, rinsed with water, and immersed in the related reaction routes at a near neutral pH. To gain a deeper sample solution under vigorous magnetic stirring to obtain insight into the reaction mechanism, the density functional a potential baseline. The potential change was then initiated by theory (DFT) calculation is adopted thereaer to explain the m adding a certain amount (200 L) of H2O2 and was determined 23,24 reaction mechanism. The obtained results were further used continuously with time. to conrm and explain the outcome of the experimental study. Computational details Experimental The density functional theory (DFT) calculation was performed 25 Chemicals and reagents using the Gaussian 16 package program. The B3LYP model together with the LanL2DZ basis set for the manganese atom Published on 26 December 2017. Downloaded by Library of Chinese Academy Sciences 9/11/2018 3:33:27 PM. Tridodecylmethylammonium chloride (TDMAC), 2-nitrophenyl and 6-31+G(d) basis set for other atoms were employed octyl ether (o-NPOE), and high-molecular weight poly(vinyl throughout this study. The solvent effect of water was taken into chloride) (PVC) were obtained from Fluka AG (Buchs, Switzer- account using the IEFPCM model. It is worth mentioning that land). Other chemicals were of analytical grade and purchased the abovementioned method has been utilized successfully in from Sinopharm Chemical Reagent Co., Ltd. (Shanghai, China). the mechanistic study of permanganate oxidation in an Aqueous solutions were prepared by dissolving the appropriate aqueous solution.20 The geometry was initially optimized, and U salts in freshly deionized water (18.2 M cm speci c resistance) the vibrational frequency was then calculated to determine the obtained using a Pall Cascada laboratory water system. The pH nature of the stationary point and the critical energy parame- measurements were conducted using a Leici pH meter coupled ters. The transition state was further conrmed by intrinsic with a combined electrode (Shanghai Apparatus Co. Ltd.) that reaction coordinate (IRC) analysis. The Cartesian coordinates was calibrated at pH 4.00, 6.86, and 9.18 before use.
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