基于离子液体的硫酸根离子选择电极的研究

将离子液体BMIMPF6应用于传感膜中制备硫酸根选择性电极,研究发现离子液体在电极中不仅能够提高传感膜的介电常数和传导速率,还与硫酸根离子发生相互作用,起到载体的功能。利用离子液体和硫脲的协同作用制备的电位传感器,对硫酸根离子在10-5～10-2 mol/L范围内有能斯特响应,同时具有pH干扰小,重复性好,响应时间快等特点,能够用于环境和生物医疗检测。     

载体型电化学传感器对有毒过渡金属离子Pb2+的检测

设计并制备了一种基于高分子聚合物(甲基丙烯酸甲酯-丙烯酸丁酯共聚物,MMA-BA)和碳纳米复合材料的固接离子选择性电极来检测水中铅离子Pb~(2+).电极使用高聚物MMA-BA作为传感膜的骨架,利用其优良的性质以及多壁碳纳米管的作用显著提高电极的传感性质.电极具有在低检测范围内的响应的特性,可将其应用在饮用水的实际检测中.     

双水杨醛乙二胺中性载体的锰离子电极的研究

研究以双水杨醛乙二胺[BBG]为中性载体,制备了一种对锰离子(Mn2 )具有优良的电位响应特性的离子选择性电极,其选择性次序为:Mn2 >>Rb ＞Al3 ＞Ca2 ＞Bi3 ＞Cu2 ＞Co2 ＞Fe3 ＞Cd2 ＞Ba2 ＞Ce3 ＞Cr3 ＞La3 ＞Na .该电极在pH 3.0的NaOH-HNO3溶液体系中具有最佳的电位响应,在1.0×10-1mol/L～ 1.0×10-5 mol/L Mn2 浓度范围呈近能斯特响应,斜率为32.0 mV/p Mn2 (25 ℃),检测下限为8.0×10-6 mol/L.采用交流阻抗和紫外光谱分析技术研究了配合物本身的结构对电极电位响应行为的作用机理.将该电极用于实际样品的测定,获得满意的结果.     

聚氯乙烯膜碘离子选择电极在溴碘离子共存体系分析中的应用

介绍了聚氯乙烯膜碘离子选择电极(PVC-I-ISE)的制备方法,电极对碘离子的能斯特响应斜率为59 mV/pI,响应的线性范围为4.0×10-5~1.0×10-2mol.L-1,检出限为1.6×10-5mol.L-1,低于用银ISE的检出限,电极的使用寿命为一个月以上。将制备的碘离子选择电极作为指示电极用于对溴、碘混合离子体系进行连续分别电位滴定,并与以银电极为指示电极的电位滴定方法进行了比较。结果表明用PVC-I--ISE作指示电极,可在I--Br-共存的混合溶液中进行两离子的连续电位滴定,而用银-ISE时则不能。     

基于石墨烯和室温离子液体复合物溶胶修饰的玻碳电极制备尿酸电化学传感器

将石墨烯(GN)与室温离子液体(IL)1-丁基-3-甲基咪唑六氟磷酸盐(BMIMPF6),以适当比例研磨成胶状IL-GN,修饰在玻碳电极(GC)上制备了IL-GN/GC。利用原子力显微镜AFM表征IL-GN的形成。由于石墨烯和室温离子液体的协同作用,该电极显示了对H2O2良好的催化性能,基于尿酸氧化酶将之制备成生物传感器,用于尿酸(UA)直接电化学检测,并进行了传感器的抗干扰性能及实际血样中尿酸的检测实验。结果表明,此传感器检测尿酸的线性范围为0.002~4.5 mmol/L,相关系数为0.995,检出限为0.85μmol/L,响应时间为10 s。此传感器制备简便,稳定性好,抗干扰能力强,可用于实际血清中尿酸的检测,为尿酸的测定提供了新方法。     

基于Schiff-base结构化合物载体的汞离子选择性电极的制备与表征

高产率合成了一种新的Schiff-base结构化合物,并将其表征为高选择性聚合物膜汞离子选择性电极载体。考察了不同增塑剂及离子交换剂对膜电极响应性能的影响,在最佳膜组分条件下测得该电极对汞离子的线性响应范围为1.0×10-6~3.0×10-4mol/L,响应斜率为(29.3±0.3)mV/dec,检出限为2.6×10-7mol/L;该电极响应速率快(小于12 s),可在较宽的pH范围内(pH2.8~5.6)使用,且其它常见碱金属、碱土金属以及过渡金属离子对该测试电极的干扰小;可准确检测自来水中汞离子的浓度。     

水杨醛缩邻苯二胺双席夫碱敏感膜Cu(Ⅱ)离子选择性电极及SCN-的测定

用水杨醛和邻苯二胺合成了水杨醛缩邻苯二胺双席夫碱（SPS）,将其作为中性载体与碳粉混合,以液体石蜡为粘合剂,制备出能斯特响应铜(Ⅱ)离子选择性电极,应用于SCN^-的测定。 SCN-浓度在1.0×10^-6~1.0×10^-2 mol/L之间时该电极对其具有能斯特响应,检测下限为4.0×10^-7 mol/L。 在pH值为3.5~4.6的SCN^-溶液中,电极的响应时间均小于30 s。电极的稳定性好,灵敏度高,使用寿命长,已用于废水中SCN^-的分析。     

Nafion雷尼替丁离子选择电极的研制及应用

本文报道了 Nafion 雷尼替丁离子选择电极的研制及其应用。该电极与一般高聚物膜传感电极相比,无需合成活性物,简化了操作过程,避免了活性物流失,延长了电极寿命,且具有较好的响应性能。用于雷尼替丁测定,线性范围为10~(-1)～5×10~(-5)mol/L。同一批号药剂测定6次,相对标准偏差为0.62%,平均回收率为99.9%。     

基于芦丁分子印迹壳聚糖-离子液体功能化石墨烯-碳纳米管的电化学传感器的制备及应用

以壳聚糖为功能单体,芦丁为模板分子,戊二醛为交联剂,离子液体功能化石墨烯-碳纳米管(GN-CNTs-IL)为掺杂材料,通过简单混合后滴加在玻碳电极表面,制备了芦丁分子印迹电化学传感器。利用扫描电镜、透射电镜及电化学技术对复合材料和印迹电极的表面形貌等进行了表征,结果发现分子印迹复合材料呈多孔结构,有良好的导电性,GN-CNTs-IL对芦丁电化学传感有明显的增敏作用。进一步对离子液体的用量、壳聚糖的浓度、壳聚糖与芦丁的质量比、溶液pH值等因素的影响进行了考察,并对制备和测试条件进行了优化。在所选条件下,所构建的电化学传感器对芦丁表现出良好的响应性能,不仅线性检测范围宽(0.01～200.0μmol/L)、检出限低(6 nmol/L),而且选择性较高、重现性好、稳定性佳。该传感器可用于荞麦茶、芦丁片等样品中芦丁的检测。     

基于电流脉冲沉积法的硝酸根微传感器研究

基于微加工技术(Microfabrication technology)制备微传感电极并进行电化学表面修饰,研制出一种用于水体中NO#3浓度检测的电化学微传感器。微传感器以两电极传感芯片为信号转换部件,使用电流脉冲沉积法在铂质工作电极表面制备微观形貌呈枝簇状的铜质敏感材料,利用铜质材料对酸性溶液中NO#3的电催化还原特性,测量还原电流的大小,实现对NO#3浓度的检测。采用扫描电子显微镜(SEM)和X射线衍射分析(XRD)技术对敏感膜进行表征和监测,探索高活性铜质敏感膜的制备方法;使用微传感器对硝酸盐标准样品进行检测,在低浓度范围(12.5~200μmol/L),响应灵敏度为0.1422μA/(μmol/L);高浓度范围(200~3000μmol/L),响应灵敏度为0.0984μA/(μmol/L),均表现出较高的检测灵敏度;使用微传感器对北京等地的实际湖库水样进行检测,结果与专业水质检测机构采用紫外分光光度法的测试结果偏差在#3.9%~15.4%之间,两者具有一定的相关性,表明微传感器能够用于实际水样中NO#3浓度的测量。     

有序介孔碳/石墨烯/镍泡沫的制备及其对多巴胺的高灵敏度和高选择性检测

柔性生物传感器在可穿戴电子设备中有着广泛的应用前景. 为了获得柔性电化学多巴胺传感器,作者在本工作中首先在镍泡沫表面通过化学气相沉积生长石墨烯,随后通过高温碳化嵌段共聚物与酚醛树脂在石墨烯表面共组装形成的薄膜制备了有序介孔碳/石墨烯/镍泡沫（OMC/G/Ni）复合材料. 其中,镍泡沫可以为复合材料提供具有高导电性和良好柔韧性的金属骨架,而具有垂直排列介孔阵列的有序介孔碳层为复合材料提供了高的电活性表面积,且有利于活性位点的暴露. 值得注意的是,夹在有序介孔碳层和镍泡沫之间的石墨烯极大地增强了各组分之间的相容性,有利于进一步提升复合材料的电化学性能. 作为电化学传感器中的工作电极,OMC/G/Ni体现出优异的多巴胺检测能力. 不但具有宽的线性检测范围（0.05 ~ 58.75 μmol·L^-1）和低检测限（0.019 μmol·L^-1）,还具有良好的选择性、重现性和稳定性. 此外,OMC/G/Ni在弯曲状态下依旧能够保持对多巴胺的高检测能力,证明了其在柔性生物传感器中的应用潜力.     

Solid contact PVC membrane electrodes based on neutral or charged carriers for the selective reading of anionic sulfamethoxazole and their application to the analysis of aquaculture water

Sulfamethoxazole (SMX) is among the antibiotics employed in aquaculture for prophylactic and therapeutic reasons. Environmental and food spread may be prevented by controlling its levels in several stages of fish farming. The present work proposes for this purpose new SMX selective electrodes for the potentiometric determination of this sulphonamide in water. The selective membranes were made of polyvinyl chloride (PVC) with tetraphenylporphyrin manganese (III) chloride or cyclodextrin-based acting as ionophores. 2-nitrophenyl octyl ether was employed as plasticizer and tetraoctylammonium, dimethyldioctadecylammonium bromide or potassium tetrakis (4-chlorophenyl) borate was used as anionic or cationic additive. The best analytical performance was reported for ISEs of tetraphenylporphyrin manganese (III) chloride with 50% mol of potassium tetrakis (4-chlorophenyl) borate compared to ionophore. Nersntian behaviour was observed from 4.0?×?10^?5 to 1.0?×?10^?2?mol/L (10.0 to 2500?µg/mL), and the limit of detection was 1.2?×?10^?5?mol/L (3.0?µg/mL). In general, the electrodes displayed steady potentials in the pH range of 6 to 9. Emf equilibrium was reached before 15?s in all concentration levels. The electrodes revealed good discriminating ability in environmental samples. The analytical application to contaminated waters showed recoveries from 96 to 106%.     

功能化有序介孔碳对重金属离子Cu(II)、Cr(VI)的选择性吸附行为

以三嵌段共聚物F127为模板剂, 酚醛树脂为碳源, 正硅酸乙酯为硅源, 三组分共组装合成介孔碳?氧化 硅纳米复合物, 再经HF去除氧化硅, 得到有序介孔碳(OMC). X射线衍射(XRD)、透射电子显微镜(TEM)、低温 N2吸脱附(BET)等测试表明, 所得样品具有高度有序的介孔结构, 比表面积和孔容分别为1330 m²·g^-1和2.13 cm³·g^-1, 平均孔径6.4 nm. 对其先氧化、后氯化、再胺化, 得到不同胺基接枝量的胺化介孔碳(C-NH₂(m), m为加入的乙二胺的质量(g)). 傅里叶变换红外(FT-IR)光谱表征结果证实, 胺基官能团成功接枝到有序介孔碳表面.TEM测试表明介孔碳的有序孔道结构得到了较好的保持. 以有序介孔碳、胺化介孔碳作吸附剂对Cu(II)、Cr(VI)进行选择性吸附研究. 结果表明: 功能化修饰前, 样品对Cu(II)、Cr(VI)饱和吸附量分别为213.33、241.55 mg·g^-1; 修饰后饱和吸附量可分别达到495.05、68.21 mg·g^-1. 功能化介孔碳表现了较强的选择性吸附Cu(II)的能力.     

Fabrication of Membrane Sensitive Electrodes for the Validated Electrochemical Quantification of Anti-Osteoporotic Drug Residues in Pharmaceutical Industrial Wastewater

Accurate and precise application of ion-selective electrodes (ISEs) in the quantification of environmental pollutants is a strenuous task. In this work, the electrochemical response of alendronate sodium trihydrate (ALN) was evaluated by the fabrication of two sensitive and delicate membrane electrodes, viz. polyvinyl chloride (PVC) and glassy carbon (GC) electrodes. A linear response was obtained at concentrations from 1 × 10⁻⁵ to 1 × 10⁻² M for both electrodes. A Nernstian slope of 29 mV/decade over a pH range of 8–11 for the PVC and GC membrane electrodes was obtained. All assay settings were carefully adjusted to obtain the best electrochemical response. The proposed technique was effectively applied for the quantification of ALN in pure form and wastewater samples, acquired from manufacturing industries. The proposed electrodes were effectively used for the determination of ALN in real wastewater samples without any prior treatment. The current findings guarantee the applicability of the fabricated ISEs for the environmental monitoring of ALN.     

Nonenzymatic glucose detection at ordered mesoporous carbon modified electrode

This work reports on a novel nonenzymatic amperometric glucose sensor based on the ordered mesoporous carbon (OMC). Amperometric method was used to evaluate the electrocatalytic activity of the OMC modified electrode toward nonenzymatic glucose in alkaline media in presence and absence of chloride ions. The results indicated that OMC showed electrocatalytic activity for the oxidation of glucose in alkaline solution. The resulting biosensor exhibited excellent performance for glucose determination with high sensitivity of 10.81 μA/mM and a low detection limit of 0.02 mM. The OMC modified electrode is also to resistant the interference from common interfering substances such as ascorbic acid, dopamine and uric acid.     

Investigation of Protein Binding With All Solid‐State Ion‐Selective Electrodes

A potentiometric sensor for studying charge based adsorption of proteins was created using a single‐piece polyaniline‐PVC ion‐selective electrode (ISE). Three different ISEs, two for Na⁺ and one for Cl^? ion determination, were studied. The Na⁺‐ISEs consisted of a neutral calixarene‐based ionophore and one with a charged carrier dinonylnapthalenesulfonic acid (DNNSA) whereas for the Cl^? ISE, an anion exchanger tridodecylmethylammonium chloride (TDDMA⁺Cl^?), was used. The Na⁺ ISE with DNNSA as the charged carrier was successfully able to discriminate the binding of two different proteins (bovine serum albumin and lysozyme) based on their intrinsic charge.     

Ruthenium(III) Schiff's Base Complex as Novel Chloride Selective Membrane Sensor

A novel chloride PVC‐based membrane sensor based on a ruthenium(III) Schiff's base complex, as an excellent neutral carrier, has been developed. The ruthenium complex, in combination with a ketonic plasticizer and a cationic additive led to ISEs with fundamental characteristics, such as slope sensitivity, short response times and selectivity coefficients, which were sufficient for practical applications. The sensor with composition of 30% PVC, 62% benzyl acetate, 5% ruthenium(III) Schiff's base complex and 3% hexadecyltrimethyl ammonium bromide displays near‐Nernstian behavior in a wide concentration range (1.0×10^?1–3.0×10^?6 M with slope of ?54.5±0.5) with a detection limit of 2.0×10^?6 M (71.0 ng per mL). The response of the electrode is independent on pH in the range of 4.0–10.0 and can it be used for at least ten weeks. The proposed electrode shows a very short response time (<20 s) in whole concentration range. The sensor displays high selectivity toward chloride ions over several organic and inorganic anions. It was successfully applied for the determination of chloride in serum samples. It was also used as an indicator electrode in the potentiometric titration of chloride ions with silver nitrate solution.     

Cobalt(II) porphyrazine as an active component of iodide-selective electrodes

Cobalt(II) porphyrazine is synthesized and studied as an active component of a polyvinyl chloride plasticized membrane ion-selective electrodes (ISEs). It is established that regardless of their structure, ISEs are sensitive to iodide. The introduction to the ISE of an ionic additive, ionic liquid 1,3-dihexadecylimidazolium chloride, significantly improves the electrochemical characteristics: the slope of the electrode function reaches ?(57 ± 1) mV/dec, c_min = 8.3 × 10^–6 M. Solid-state screen-printed electrodes the surfaces of which are modified by a 1: 4 mixture of cobalt(II) porphyrazine and ionic liquid 1,3-dihexadecylimidazolium chloride demonstrate satisfactory electrochemical characteristics: the slope of the electrode function is ?(56 ± 4) mV/dec and c_min = 2.5 × 10^–5 M. The potentiometric selectivity of the ISEs for iodide is studied. It is found that the effect of lipophilic interfering ions is significantly lower for solid state ISEs than for plasticized membrane electrodes.     

Potassium sodium chloride integrated microconduits in a potentiometric analytical system

The preparation and application of a K(+), Na(+) and Cl(-) integrated microconduit potentiometric analytical system with tubular ion-selective electrodes (ISEs), microvalve, chemfold, electrostatic and pulse inhibitors is described. Electrochemical characteristics of the tubular ISEs and integrated microconduit FIA-ISEs were studied. The contents of K(+), Na(+) and Cl(-) in soil, water and serum were determined with the device. The analytical results agreed well with those obtained by flame photometric and silver nitrate volumetric methods.     

Solid-contact ion-selective electrodes for aromatic cations based on pi-coordinating soft carriers

Ion-selective electrodes (ISEs) based on pi-coordinating carriers were prepared and investigated as potentiometric sensors for aromatic cations, using N-methylpyridinium as a model aromatic cation. Derivatives of tetraphenylborate were studied as charged carriers in plasticized poly(vinyl chloride) membranes. Furthermore, neutral compounds containing pi-coordinating anthryl groups were studied as neutral carriers. Bis(2-ethylhexyl)sebacate (DOS) and 2-nitrophenyl octyl ether (o-NPOE) were used as non-polar and polar plasticizer, respectively. ISEs were constructed by using poly(3,4-ethylenedioxythiophene) (PEDOT) as solid-contact material. Conventional ISEs with internal filling solution were used for comparison. The potentiometric responses of the ISEs were investigated using N-methylpyridinium as primary ion. The results show that the selectivity of the ISEs is influenced significantly by both the plasticizer and the charged carriers, while the neutral carriers studied have only a minor influence on the selectivity. The role of cation-pi interactions between aromatic cations and the membrane components is discussed.