Synthesis of an ammonium ionophore and its application in a planar ion-selective electrode

A modular technique was used to synthesize an ammonium-selective ionophore based on a cyclic depsipeptide structure. The ionophore was incorporated into a planar ion-selective electrode sensor format and the selectivity tested versus a range of metal cations in a commercial clinical diagnostic "point-of-care" instrument. Four sensor membrane formulations were tested, all of which consisted of plasticized PVC. Formulations differed as to the type of plasticizer used and whether an ionic additive was present. It was found that the membrane containing the polar plasticizer nitrophenyl octyl ether in the absence of ionic additive exhibited near-Nernstian behavior (slope, 60.1 mV/decade at 37 degrees C) and possessed high selectivity for ammonium ion over lithium and the divalent cations, calcium and magnesium (log K(POT)NH4+(j) = -7.3, -4.4, and -7.1 for lithium, calcium, and magnesium ions, respectively). The same membrane also exhibited sodium and potassium selectivity that was comparable to that reported for nonactin (log K(POT)NH4+(j) = -2.1 and -0.6 for sodium and potassium, respectively, compared to -2.4 and -0.9 in the case of nonactin). Membranes containing the less polar plasticizer, dioctyl phthalate, showed sub-Nernstian behavior (slope, <50 mV/decade at 37 degrees C). In all cases, the presence of the ionic additive potassium tetrakis(4-chlorophenyl)borate substantially reduced the selectivity observed. The flexible modular synthetic technique developed and reported here will allow the cyclic depsipeptide structure to be tuned for optimum selectivity.     

Design and synthesis of sodium ion-selective ionophores based on 16-crown-5 derivatives for an ion-selective electrode

To develop an ionophore that is highly selective for sodium for use in an ion-selective electrode, we propose a model based on 16-crown-5 which has a cavity just the size of Na(+ )and has a "block" subunit to prevent complex formation with ions larger than Na(+). Based on this molecular model, eight kinds of 16-crown-5 derivatives have been synthesized, and their structural ion selectivity has been evaluated in detail. The 16-crown-5 derivatives having two bulky "block" subunits showed high Na(+) selectivity relative to K(+). In particular, the derivative with two decalino subunits (DD16C5) exhibited the highest Na(+) selectivity of all the ionophores examined. When a phosphate ester-type membrane plasticizer, tris(ethylhexyl) phosphate, was used as the membrane solvent for the ion-sensing membrane based on poly(vinyl chloride), the electrode using DD16C5 exhibited a Na(+) selectivity of over 1000 times relative to alkali metal and alkaline earth metal ions, including K(+), which is the most serious interferant. The evaluation of the relationship between the ionophore chemical structures and the ion-selective features contributes to the host-guest chemistry to give a highly selective ionophore for an alkali metal ion.     

基于伏安型离子选择性电极的pH检测研究

将含有电活性物质的离子选择性膜直接滴涂在玻碳电极上,制成一种新型伏安型离子选择性电极(VISE)。通过在电极上施加循环伏安信号,提取电活性物质的还原峰电位可实现待测离子的定量分析。将这种VISE应用于pH检测,分别考察VISE的pH响应特性、离子选择性、实际样检测能力以及对积累电荷的抗干扰能力。结果表明:基于循环伏安法的VISE在pH检测中具有较好的准确性、灵敏度、重复性和离子选择性,可用于实际样品的检测。相比于基于电位分析法的传统离子选择性电极(ISE),可不受电荷积累的影响,在水质的实时在线监测中具有较好的应用前景。     

An ion-selective electrode for acetate based on a urea-functionalized porphyrin as a hydrogen-bonding ionophore

An ion-selective electrode for acetate based on (α,α,α,α)-5,10,15,20-tetrakis[2-(4-fluorophenylureylene)phenyl]porphyrin as an ionophore that has no metal center and forms hydrogen bonds to the analyte is described. At pH 7.0 (0.1 M HEPES-NaOH buffer), the electrode based on this ionophore and cationic sites (50 mol % relative to the ionophore) responds to acetate in a linear range from 1.58 × 10(-)(4) to 1.58 × 10(-)(2) M with a slope of -54.8 ± 0.8 mV/decade and a detection limit of (3.06 ± 1.15) × 10(-)(5) M. Selectivity coefficients determined with the separate solution method (SSM) indicate that interferences of hydrophobic inorganic anions are relatively small (log[Formula: see text] (SSM): NO(3)(-), +0.68; SCN(-), +0.60; NO(2)(-), +0.22; I(-), +0.20; ClO(4)(-), +0.12; Br(-), -0.13). Responses to anions that are good hydrogen bond acceptors, i.e., Cl(-), HSO(3)(-), and HCO(3)(-), were Nernstian and were weaker than the response to acetate (log[Formula: see text] (SSM): -0.54, -0.56, and -1.34, respectively). Negligibly small responses were observed for very hydrophilic anions, i.e., F(-), SO(4)(2)(-), and H(2)PO(4)(-)/HPO(4)(2)(-). While aliphatic carboxylates such as formate, propanoate, pyruvate, and lactate gave Nernstian responses similar to acetate, interferences of salicylate and benzoate were considerably decreased in comparison with electrodes based on cationic sites only. Concentrations of acetic acid in vinegar samples were determined by direct potentiometry and agreed with values determined by a standard enzymatic method.     

Application of electrochemically reduced graphene oxide on screen-printed ion-selective electrode

In this study, a novel disposable all-solid-state ion-selective electrode using graphene as the ion-to-electron transducer was developed. The graphene film was prepared on screen-printed electrode directly from the graphene oxide dispersion by a one-step electrodeposition technique. Cyclic voltammetry and electrochemical impedance spectroscopy were employed to demonstrate the large double layer capacitance and fast charge transfer of the graphene film modified electrode. On the basis of these excellent properties, an all-solid-state calcium ion-selective electrode as the model was constructed using the calcium ion-selective membrane and graphene film modified electrode. The mechanism about the graphene promoting the ion-to-electron transformation was investigated in detail. The disposable electrode exhibited a Nernstian slope (29.1 mV/decade), low detection limit (10(-5.8) M), and fast response time (less than 10 s). With the high hydrophobic character of graphene materials, no water film was formed between the ion-selective membrane and the underlying graphene layer. Further studies revealed that the developed electrode was insensitive to light, oxygen, and redox species. The use of the disposable electrode for real sample analysis obtained satisfactory results, which made it a promising alternative in routine sensing applications.     

关于用离子选择电极法测定植物中氟化物的探讨

采用离子选择电极法测定植物中的氟化物:植物样品先用0.05mol/L硝酸溶液浸提,然后再用0.1mol/L氢氧化钾溶液继续浸提,用氟离子选择性电极法来测定;该方法具有精密度和回收率都较好的特点。     

Effect of the phase volume ratio on the potential of a liquid-membrane ion-selective electrode

Two-phase liquid system IA(w)|IX(o) comprising the interface between the aqueous solution (w) of uni-univalent electrolyte IA and an organic solvent solution (o) of a uni-univalent electrolyte IX with the common cation I(+) is considered as a simple model of a liquid-membrane ion-selective electrode (ISE). Taking into account the electroneutrality and mass balance conditions, the equilibrium Galvani potential difference (pd) between the aqueous and organic phases, phi = phi(w) - phi(o), is calculated numerically as a function of the ratio of the initial electrolyte concentrations, x = / = 10(-)(4)-10(4), for the selected values of the phase volume ratio r = V(o)/V(w) = 10(-)(3), 1, and 10(3), and the standard ion transfer potentials of the present ions ranging from -0.5 to 0.5 V. Numeric results corroborate the symbolic expressions derived for the cases when X(-) and A(-) are extremely lipophilic and hydrophilic ions, respectively, or when the concentration ratio x is extremely large or small. In contrast to the extraction system, where both electrolytes are initially present in the aqueous phase, the effect of the phase volume ratio on the equilibrium pd in the ISE model is rather weak, unless the counterions X(-) and A(-) differ little in their lipophilicity from the target ion I(+). It is shown that both the ISE and extraction model exhibit the Nernstian behavior only in a limited range of the concentration ratio x depending on the value of the standard ion transfer potentials of the counterions. When this ratio is extremely large or small, equilibrium pd approaches the limiting value given by the distribution potential of the electrolyte IA or IX, respectively. Similar conclusions can be drawn for the two-phase liquid system AI(w)|XI(o) with the common anion I(-).     

A chronoamperometric method to estimate ionophore loss from ion-selective electrode membranes

A novel chronoamperometric method was developed to estimate the concentration of a neutral ionophore in fixed-site, dioctyl sebacate plasticized, poly(vinyl chloride)-based, ion-selective electrode membranes. The membranes contained between 0.5 and 16 mmol/kg valinomycin. The chronoamperometric technique was used to estimate the valinomycin concentration in freshly prepared membranes and after extraction of some of the ionophore from the membranes using dioctyl sebacate. Replicate measurements indicated a relative standard deviation in the calculated valinomycin concentration of less than 10%, and these values accurately represented the true concentration of valinomycin within 10%. The method permitted an estimate of the valinomycin concentration after valinomycin was leached from a membrane. The results of preliminary experiments using heparinized dog blood suggest that blood protein adsorption does not interfere qualitatively or quantitatively with the analysis.     

Reducing the thrombogenicity of ion-selective electrode membranes through the use of a silicone-modified segmented polyurethane.

The susceptibility of segmented polyurethanes (SPUs) to in vivo oxidative cleavage and hydrolysis constitutes a drawback in the use of these materials in the fabrication of implantable devices. The introduction of poly(dimethylsiloxane) (PDMS) groups into the polymer main chain has been previously reported to enhance the stability of SPUs. Herein, we evaluated the use of BioSpan-S, a silicone-modified SPU, in the design of membranes for cation-selective electrodes. The resulting electrodes exhibited good potentiometric response with all of the tested ionophores (valinomycin, sodium ionophore X, and nonactin). The obtained selectivity coefficients meet the selectivity requirements for the determination of sodium and potassium in blood. Moreover, as reflected by SEM studies, membranes prepared with BioSpan-S showed less adhesion of platelets than membranes prepared with conventional poly(vinyl chloride) (PVC). These results lead to the conclusion that BioSpan-S would be an appropriate candidate for the fabrication of implantable ion-selective electrodes.     

Potentiometric properties of ion-selective electrode membranes based on segmented polyether urethane matrices

Potentiometric responses of polyurethane (PU)-based membranes containing valinomycin and varying amounts of plasticizer (DOA) and/or lipophilic additive (KTpClPB) were examined as a function of soft segment [poly(tetramethylene ether glycol)] contents in aromatic diisocyanate-based PU matrices. Upon increasing the weight percentages (w(soft)) of soft segments, which in part behave like a built-in plasticizer, providing the matrices with rubbery structure (glass transition temperature below -58 °C), the amounts of DOA and/or KTpClPB necessary to result in near-Nerntian response (e.g., slope > 50 mV/decade) to potassium were substantially lowered. The apparent effect of adding plasticizer to PU-based membranes was comparable to that resulting from an increase of free carrier concentration in normal PVC-based membranes. Owing to the chemical interaction between mobile anionic sites and urethane chains, plasticizer-free PU membranes could be prepared with the PU matrices with high soft segment contents (w(soft) ≥ 60 wt %). PUs composed of 60 ≤ w(soft) < 80 wt % were recommended as the matrix for fabricating ISE membranes with no or low plasticizer content.     

MXene修饰碳纤维电极的制备及其超级电容器性能研究

近年来,柔性储能设备因便携、可穿戴性而受到广泛关注,二维过渡金属碳化物MXene因其具有优良的储能性能和柔韧性而被广泛的运用于柔性储能系统。采用冷冻干燥的方法,使分散的MXene纳米片层吸附在酸化后的碳纤维表面,通过碳纤维不同的酸化时间、MXene浸渍次数和不同的溶液浓度下进行处理。采用SEM、FT-IR、XRD观察对比不同处理条件下碳纤维微观物理化学结构的变化情况,同时采用电化学工作站对不同处理条件下碳纤维复合电极的储能性能进行探讨。结果表明,选择合适的酸化时间,浸渍次数和溶液浓度条件,能够使MXene纳米片层牢固有效的附着在碳纤维表面,有效提升复合电极的电化学储能性能,在合适的处理条件下,碳纤维复合电极的比电容可达到70.9 F/g。复合电极组装超级电容器,其比电容有12.8 F/g,是烧蚀CF样品的6倍。     

Calcium ion-selective electrode based on the facile synthesis of CuO over Cu wires

Here, we report a simple, cost-effective and repeatable process to grow copper(II) oxide (CuO) over a Cu wire. Characterization of the prepared CuO structures revealed a pure phase of CuO with high-density nanostructures. By applying dibenzo-18-crown-6 as an ionophore, CuO (as a solid contact, SC) was developed into a calcium (Ca²⁺) ion-selective electrode (ISE) with a linear activity range between 10 μM and 100 mM, an average Nernstian slope (sensitivity) of 32.3?±?1.3 mV/decade, and a lower limit of detection (LOD) of 10 μM. When tested for selectivity among three ions (magnesium, nickel, and sodium) in addition to the target ion, the electrode had better selectivity toward Ca²⁺ ions. We were able to demonstrate that the proposed Cu/CuO electrode was stable within the pH range from 5.0 to 9.0 for a period of 60 days. Our results of the proposed SC-ISE exhibit a good potential response and acceptable stability, and they show a clear indication that Cu/CuO nanostructures (SC-ISE) can be used as an ion-to-electron transducer for low-cost solid-state potentiometric sensors.

     

氯碱电解液离子选择电极浓度分析实验研究

应用离子选择电极分析氯碱电解液氯离子浓度，通过分析，氯碱电解液中的共存离子对测量测量影响可忽略不计。理论分析与实验结果均表明，离子电极测定电解液中氯离子浓度精密度与测量精度均较高，该测量方法测量速度快，人为误差小，易实现自动化测量，具有一定的实用价值。     

Speciation of aluminum in rainwater using a fluoride ion-selective electrode and ion-exchange chromatography with fluorometric detection of the aluminum-lumogallion complex

Soluble aluminum in rainwater was separated into three categories: free aluminum (Al3+), fluoride complexes (sum of AlF2+ and AlF2+), and other forms of aluminum. The free form of the aluminum ion (Al3+) was directly obtained from the separation data of aluminum species according to their charge using gradient elution cation-exchange chromatography. The aluminum fluoride complexes were estimated by combining the data of the free and total fluoride determined using a fluoride ion-selective electrode, with the assumption that 2+ charged aluminum species consisted only of AlF2+. The rest of the aluminum species had a 1+, neutral, or negative charge and mainly consisted of organic complexes. The origin of the organically bound aluminum is discussed. The concentration range of the total dissolved fluoride and aluminum in the rainwater samples was usually in the micromolar to submicromolar range, and the ratio of [T-F]/[T-Al] was found to be between 1 and 4. The speciation of dissolved aluminum into three categories was carried out on the basis of data of 15 rainwater samples collected in the city of Otsu.     

Stripping analysis of nanomolar perchlorate in drinking water with a voltammetric ion-selective electrode based on thin-layer liquid membrane

A highly sensitive analytical method is required for the assessment of nanomolar perchlorate contamination in drinking water as an emerging environmental problem. We developed the novel approach based on a voltammetric ion-selective electrode to enable the electrochemical detection of "redox-inactive" perchlorate at a nanomolar level without its electrolysis. The perchlorate-selective electrode is based on the submicrometer-thick plasticized poly(vinyl chloride) membrane spin-coated on the poly(3-octylthiophene)-modified gold electrode. The liquid membrane serves as the first thin-layer cell for ion-transfer stripping voltammetry to give low detection limits of 0.2-0.5 nM perchlorate in deionized water, commercial bottled water, and tap water under a rotating electrode configuration. The detection limits are not only much lower than the action limit (approximately 246 nM) set by the U.S. Environmental Protection Agency but also are comparable to the detection limits of the most sensitive analytical methods for detecting perchlorate, that is, ion chromatography coupled with a suppressed conductivity detector (0.55 nM) or electrospray ionization mass spectrometry (0.20-0.25 nM). The mass transfer of perchlorate in the thin-layer liquid membrane and aqueous sample as well as its transfer at the interface between the two phases were studied experimentally and theoretically to achieve the low detection limits. The advantages of ion-transfer stripping voltammetry with a thin-layer liquid membrane against traditional ion-selective potentiometry are demonstrated in terms of a detection limit, a response time, and selectivity.     

SWCNT-DNA修饰电极的制备及其电化学检测性能

利用单壁碳纳米管(SWCNT)与单链DNA(ssDNA)自组装生成单根离散的sWCNT-DNA复合物,将其吸附在玻炭(GC)电极表面形成一层SWCNTT-DNA薄膜,构建SWCNT-DNA修饰玻炭电极.循环伏安测试表明,与裸玻炭电极和未分散SWCNT修饰的玻炭电极相比,该电极的响应峰电流明显增大,而且在一定范围内对不同浓度的铁氰化钾有一个线性响应,表现出良好的灵敏度和稳定性.ssDNA通过缠绕在SWCNT外壁使其离散,可提高电极的有效表面积,加快Fe(CN)3-6/Fe(CN)4-6-氧化还原反应的电子传递,使之表现出良好的电化学检测性能.     

An analogy of an ion-selective electrode sensor based on the voltammetry of microcrystals of tetracyanoquinodimethane or tetrathiafulvalene adhered to an electrode surface

The voltammetry of solid 7,7,8,8-tetracyanoquinodimethane (TCNQ) and tetrathiafulvalene (ITF) at an electrode-microparticle-aqueous (electrolyte) interface generates characteristic current-potential profiles associated with solid-solid-phase transformations. During the reactions, electrolyte ions are included into the TCNQ (cations) and TTF (anions) lattice sites as part of the charge neutralization process. Consequently, electrolyte ion concentration is associated with the reversible potential of the TCNQ0/- and TTF0/+ reactions, making these processes candidates for the development of novel voltammetric cation and anion sensors, respectively. Electrode potential-analyte ion concentration dependence studies exhibited highly reproducible potential shifts of 45 (+/- 1) mV/decade change in ion analyte concentration for both the TCNQ cation sensor and the TTF anion sensor. When presented with mixed-analyte solutions, both ion-sensing systems exhibited a degree of ion selectivity. Ion selectivity trends may be modeled using equations based on a Nicolsky-type selectivity relationship, in accordance with the concept that these are the voltammetric analogies of potentiometric ion-selective membrane electrodes.     

Preparation and electrochemical properties of nickel oxide as a supercapacitor electrode material

Hydrothermal synthesis has been introduced to fabricate NiO precursor at different temperatures, then nanostructured NiO with a distinct flake-like morphology was obtained via heating at low temperature. The NiO nanoflakes are 50-80 nm in width and 20 nm in thickness. The electrochemical capacitive characterization of the as-prepared NiO was studied in 2 M KOH electrolyte solution. The as-prepared NiO exhibits excellent cycle performance and keeps 91.6% initial capacity over 1000 charge-discharge cycles. Electrochemical impedance spectroscopy study reveals that the NiO electrode is controlled by the mass transfer limitation, and its internal resistance is 0.2 Ω. A specific capacitance approximate to 137.7 F g⁻¹ could be achieved at the current density of 0.2 A g⁻¹ in the potential window of 0-0.46 V in 2 M KOH electrolyte solution, due to higher surface area of NiO nanoflakes, which facilitates transport of electrolyte ions during rapid charge/discharge process. Due to higher surface area of NiO nanoflakes, which facilitates transport of electrolyte ions during rapid charge/discharge process.     

硫氮共掺杂石墨烯修饰电极的制备及电化学性能研究

以天然鳞片石墨为原料,采用改进的Hummers法制备了氧化石墨(GO),以GO和硫氰酸铵为前驱体,采用一步水热法制备了硫氮共掺杂石墨烯(SNG)。X射线衍射、扫描电子显微镜和拉曼光谱分析结果显示,硫和氮成功掺入石墨烯晶格中,SNG表面褶皱明显且形成了三维孔道结构。通过交流阻抗、循环伏安法和差分脉冲伏安法考察了对苯二酚(HQ)、邻苯二酚(CC)和间苯二酚(RC)在修饰玻碳电极(SNG-180/GCE)上的电化学行为。结果表明:硫氮共掺杂能有效改善石墨烯的电化学性能,修饰电极实现了对HQ、CC和RC的同时检测,线性范围在5.5~43.06μmol/L和90.91~245.28μmol/L之间,检出限为1.83μmol/L(信噪比为3)。