Construction of a highly selective PVC-based membrane sensor for Ce(III) ions

A highly Ce(III) ion-selective poly vinyl chloride (PVC) membrane sensor based on N′-[(2-hydroxyphenyl)methylidene]-2-furohydrazide (NHMF) as an excellent sensing material is successfully developed. The electrode shows a good selectivity for Ce(III) ions with respect to most common cations including alkali, alkaline earth, transition and heavy metal ions. The proposed sensor exhibits a wide linear response with a slope of 19.4 ± 0.3 mV/decade over the concentration range of 1.0 × 10⁻⁵ to 1.0 × 10⁻¹ M, and a detection limit of 7.6 × 10⁻⁶ M of Ce(III) ions. The sensor response is independent of pH in the range of 3.5–10.0. The proposed electrode was applied as an indicator electrode in potentiometric titration of Ce(III) ions with EDTA and C₂O₄². It was also successfully applied in the determination of cerium ions in aqueous samples.     

Nano levels detection of beryllium by a novel beryllium PVC-based membrane sensor based on 2,3,5,6,8,9-hexahydro-1,4,7,10-benzotetra oxacyclododecine-12-carbaldehyde-12-(2,4-dinitrophenyl)hy

A novel poly(vinyl chloride)-based 2,3,5,6,8,9-hexahydro-1,4,7,10-benzotetra oxacyclododecine-12-carbaldehyde-12-(2,4-dinitrophenyl)hy (PBC) with sodium tetraphenyl borate (NaTPB) as an anion excluder, benzyl acetate (BA), acetophenon (AP) and o-nitrophenyloctyl ether (NPOE) as plasticizing solvent mediators was prepared and investigated as a beryllium selective sensor. The best performance was observed with the membrane having the PVC–NaTPB–NPOE–PBC composition 30%:3%:62%:5%, which worked well over a very wide concentration range (1.0×10⁻⁷ M to 1.0×10⁻¹ M). The sensor exhibits a Nernstian slope of 29.9 mV per decade of Be²⁺ activity. The detection limit of the sensor is 7.0×10⁻⁸ M (630 ppt). The proposed electrode shows excellent discriminating ability toward Be²⁺ ion with regard to alkali, alkaline earth, transition and heavy metal ions. It was successfully applied to the determination of beryllium in a mineral sample.     

香草醛缩氨基硫脲为中性载体的铬离子选择性电极的研究

合成了香草醛缩氨基硫脲并以此做中性载体研制了PVC膜铬离子选择性电极。在pH=3.0的硝酸体系中,电极电位呈现近能斯特响应,线性响应范围为3.0×10-5～1×10-1mol/L,斜率为20.8mV/dec(20℃),检测下限为1.5×10-5mol/L。电极具有较好的稳定性和重现性。该电极用于EDTA的电位滴定其结果令人满意。     

Electrochemical copper (II) sensor based on self-assembled 4-amino-6-hydroxy-2-mercaptopyrimidine monohydrate

A 4-amino-6-hydroxy-2-mercaptopyrimidine monohydrate (AHMP)-based self-assembled monolayer (SAM) was formed on the gold electrode surface. Ellipsometric measurements evidenced the SAM formation on the gold electrode surface. The structural integrity of the modified gold electrode was also characterized by insulating properties of the SAM that were detected by cyclic voltammetry. The results of cyclic voltammetry showed that the SAM, which was formed by assembly of AHMP, was stable but did not completely block the redox-activity of ferrocene and K₃[Fe(CN)₆]/K₄[Fe(CN)₆]. In contrast completely blocked redox-activity was observed after the treatment of AHMP-based SAM with saturated solution of 4-formylphenylboronic acid in 1,4-dioxan. The modified electrodes exhibited a selective response towards Cu(II) ions in the presence of some interfering ions such as Cd(II), Co(II), Fe(II), Ni(II) and Pb(II). This study is the first scientific report on the application of AHMP-modified electrode as a selective Cu(II) sensor in the presence of some interfering cations.     

Perchlorate selective membrane electrodes based on synthesized platinum(II) complexes for low-level concentration measurements

Three synthesized platinum(II) complexes, [PtR₂(NN)] (R = Me, p-MeC₆H₄ and p-MeOC₆H₄; NN = 2,2′-bipyridyl), were studied to characterize their ability as an anion carrier in a PVC membrane electrode. The polymeric membrane electrodes (PME) and also coated glassy carbon electrodes (CGCE) prepared with [Pt(p-MeOC₆H₄)₂(NN)] showed excellent response characteristics to perchlorate ions. The electrodes exhibited Nernstian responses to ClO₄⁻ ions over a wide concentration range from 5 × 10⁻⁷ to 4.0 × 10⁻¹ M for PME and 1.5 × 10⁻⁷ to 2.7 × 10⁻¹ M for CGCE with low detection limits (4.0 × 10⁻⁷ M for PME and 1.0 × 10⁻⁷ M for CGCE). The electrodes possess fast response time, satisfactory reproducibility, appropriate lifetime and, most importantly, good selectivity toward ClO₄⁻ relative to a variety of other common anions. The potentiometric response of the electrodes is independent of the pH of the test solution in the pH range 2.5–9.5. The proposed sensors were used in potentiometric determination of perchlorate ions in mineral water, urine samples and also samples containing interfering anions. The interaction of the ionophore with perchlorate ions was shown by UV–vis spectroscopy.     

Characterisation of an optical sensor membrane based on the metal ion indicator Pyrocatechol Violet

A non-specific photometric metal ion indicator Pyrocatechol Violet (PV) was tested for its potential use in a metal-sensitive optrode membrane. The water soluble indicator was lipophilised in the form of an ion pair with tetraoctylammonium cation (TOA), and subsequently immobilised in a plasticised PVC membrane. The spectral response of the membrane in the presence of various transition metal ions was studied. It was found that the ability of PV to form complexes with metal ions significantly reduced following immobilisation, with the exception of Cu(II). A number of factors responsible for the improved selectivity and high sensitivity of immobilised PV towards Cu(II) were identified. Amongst those, the most important is the presence of quaternary ammonium salt in the membrane which induced a significant bathochromic shift of the PV–Cu(II) chelate absorption maximum, as well as the intensification of the chelate absorption band. The membrane responds to Cu(II) irreversibly by changing colour from yellow to green (absorption maximum at 740 nm), and typically, an exposure time of 10 min enables the determination of Cu(II) in the 1–100 μM range. A comparison of selectivity and sensitivity characteristics between the water soluble form of the indicator and the immobilised form was performed, and the effects of pH and lipophilic surfactant additives on the response mechanism are discussed.     

Potential of 5,10,15,20-Tetrakis(3′,5′-di-tertbutylphenyl)porphyrinatocopper(II) for a multifunctional sensor

An organic compound 5,10,15,20-Tetrakis(3′,5′-di-tertbutylphenyl)porphyrinatocopper(II) (TDTPPCu) is synthesized and studied as an active material for multifunctional capacitive sensor. The capacitance of the device as a function of illumination, humidity and temperature has been investigated. It is observed that the capacitance increases by 4.7 times from the dark condition under an illumination of 3850 lx. The capacitance is also changed 9.5 times with the increase in relative humidity (RH) from 30% to 95%. No change in capacitance appeared below critical temperature 120 °C. Based on the experimental results for the multifunctional sensor a mathematical model has been developed. The model is mainly based on the assumption that the capacitive response of the sensor is associated with dielectric polarization. The sensors are simulated using this model. The simulated results match well with experimental results.     

基于Si_3N_4薄膜的压力传感器

采用微机电系统(MEMS)技术制造的传感器具有体积小、重量轻、成本低等特点。基于S i3N4压力敏感膜,利用MEMS技术,设计了一种用于测量气压的传感器。采用应变电阻原理对压力进行测量,进行了理论分析计算,设计了工艺过程,制作出了器件样片。这种压力传感器的显著优点是结构简单、工艺过程容易。并且,在50~100 kPa的压力条件下,对传感器进行了测试,其精度达到了0.5%。     

Li2CO3-YSZ-SrCO3敏感电极的CO2电化学传感器研究

借助X射线衍射(XRD),扫描电镜(SEM)分析方法,研究以Li2CO3-YSZ-SrCO3作为敏感电极的氧化锆(YSZ)固体电解质CO2传感器.结果表明,在实验条件(450℃,CO2浓度(34 100 ～ 576 800)×10-6)下,传感器对CO2浓度变化具有准确、快速的响应.Li2CO3-YSZ-SrCO3电极烧制温度对其性能有影响.750℃烧制时,ZrO2与Li2CO3和SrCO3反应较充分;725℃烧制时,反应较浅.比较而言,725℃烧制的传感器响应较好.     

DPSV法快速测定茶叶中Pb的SPCE传感器的研究

为探究出一种食品（茶）中Pb的快速检测新技术,研究以丝网印刷碳电极为支持电极,选用差分脉冲溶出伏安法和电极同位镀汞膜法,以多种绿茶作为固体有机物食物代表的检测对象,进行痕量Ph的快速检测研究。优化同位镀汞膜浓度、时间、最佳底液、沉积电位等6项最佳条件参数。在优化条件下,溶出峰电流与Pb浓度在10-300μg／L范围内呈现良好的线性关系,检出限为2．208μg/L。茶样检测结果其标准偏差小于8％,回收率达到85．2％～109．3％。实验结果表明：研究出的丝网印刷传感器差分脉冲伏安法测定茶叶中的Pb离子具有快速、灵敏、准确、经济等优点,所用丝网印刷传感器可实现一次性使用和批量生产。     

Enantioselective, potentiometric membrane electrodes based on cyclodextrins for the determination of l-histidine

Four enantioselective, potentiometric membrane electrodes based on carbon paste impregnated with α-, β-, 2-hydroxyl-3-trimethylammoniopropyl-β-(as chloride salt) and γ-cyclodextrins (γ-CDs) are proposed for the assay of l-histidine (l-his). The proposed electrodes showed near-Nernstian response over l-his but not over d-histidine (d-his). The recovery of l-his in the presence of d-his was higher than 99.10% with R.S.D. lower than 0.1%. The surfaces of the electrodes are easily renewable by simply polishing on an alumina paper.     

Fabrication of a highly selective and sensitive Gd(III)-PVC membrane sensor based on N-(2-pyridyl)-N′-(4-nitrophenyl)thiourea

In this work we report the development of a highly selective and sensitive Gd(III) membrane based on N-(2-pyridyl)-N′-(4-nitrophenyl)thiourea (PyTu4NO₂) as an excellent neutral ion carrier. The Gd(III) sensor exhibits a Nernstian slope of 19.95 ± 0.3 mV per decade over the concentration range of 3.0 × 10⁻⁷ to 1.0 × 10⁻¹ M, and a detection limit of 3.0 × 10⁻⁷ M of Gd(III) ions. The potentiometric response of the sensor is independent of the solution pH in the range of 4.0–9.0. It manifests advantages of low detection limit, fast response time (10 s), and most significantly, very good selectivity with respect to a number of lanthanide ions (La, Ce, Sm, and Eu ions). It can be used at least for a period of 8 weeks without any significant divergences in its potential response. To assess its analytical applicability the proposed Gd(III) sensor was successfully applied as an indicator electrode in the titration of Gd(III) ion solutions with EDTA and for the determination of the fluoride ion in two mouth wash preparations. It was also used for the direct monitoring of Gd(III) ions in binary mixtures.     

Potentiometric sensor based on molecularly imprinted polymer for determination of melamine in milk

A polymeric membrane ion-selective electrode for determination of melamine is described in this paper. It is based on a molecularly imprinted polymer (MIP) for selective recognition, which can be synthesized by using melamine as a template molecule, methacrylic acid as a functional monomer and ethylene glycol dimethacrylate as a cross-linking agent. The membrane electrode shows near-Nernstian response (54 mV/decade) to the protonated melamine over the concentration range of 5.0 × 10⁻⁶ to 1.0 × 10⁻² mol L⁻¹. The electrode exhibits a short response time of 16 s and can be stable for more than 2 months. Combined with flow analysis system, the potentiometric sensor has been successfully applied to the determination of melamine in milk samples. Interference from high concentrations of ions co-existing in milk samples such as K⁺ and Na⁺ can be effectively eliminated by on-line introduction of anion- and cation-exchanger tandem columns placed upstream, while melamine existing as neutral molecules in milk of pH 6.7 can flow through the ion-exchanger columns and be measured downstream by the proposed electrode in an acetate buffer solution of pH 3.7.     

A polymer lab chip sensor with microfabricated planar silver electrode for continuous and on-site heavy metal measurement

This paper presents a reusable polymer lab chip sensor for continuous and on-site heavy metal monitoring in nature. In particular, detection of lead (Pb(II)), which is the most common heavy metal pollutant, has been performed using the proposed lab chip sensor. The miniaturized lab chip sensor consists of a microfabricated silver working electrode that replaces the conventional mercury and bismuth electrodes, an integrated silver counter and quasi-reference electrode, and microfluidic channels. The proposed sensor targets on-site environmental monitoring in a continuous fashion without disturbing or contaminating the sensing environment when it is reused. The reusability of the miniaturized lab chip sensor was characterized through forty-three consecutive measurements in non-deoxygenating standard solutions inside the microchannels using square-wave anodic stripping voltammetry (SWASV). With only 13.5 μL of sample volume the sensor chip showed a correlation coefficient of 0.998 for the Pb(II) concentration range of 1-1000 ppb with the limit of detection of 0.55 ppb at 300 s deposition time. The peak potentials during the forty-three consecutive SWASV measurements showed a relative standard deviation of 1.0%, with a standard deviation of 0.005 V. The high repeatability and linearity of the sensor over the large, three orders of magnitude, dynamic range of 1-1000 ppb showed that the developed sensor chip can be reused for a variety of on-site measurements such as for soil pore water or groundwater, using only micro-volumes.     

六维力传感器下E膜小生境野草EKF滤波研究

为减小噪声信号对六维力传感器测量精度的影响,同时解决因主振型信息缺失导致扩展Kalman滤波器难以获得最优系统估计的问题,提出一种基于小生境野草算法优化的扩展卡尔曼滤波（NIWO-EKF）算法。算法根据正弦激励力响应与应变之间的关系,构建六维力传感器下E型膜非线性系统模型。将系统干扰矩阵与控制矩阵视为一个整体,引入野草繁殖思想,以前6阶主振型信息构成的综合矩阵为均值,进行高斯采样,产生初始化的可行解。将小生境技术与野草算法相融合,利用野草算法进行全局搜索,根据适应度的大小对个体进行降序排列,按照小生境容量划分出多个种群协同合作,避免搜索过程陷入局部最优,提高算法的寻优精度和收敛速度。采用改进野草算法对EKF中的系统干扰控制矩阵进行优化处理。仿真实例表明,优化后的扩展卡尔曼滤波器能有效地提高六维力传感器的测量精度,具有很好的鲁棒性和稳定性。     

纳米孔Al2 O3修饰Si基氨气传感器设计

针对Si基微结构气体传感器中Si基与敏感材料之间附着性较差的问题,提出在Si基与敏感材料之间引入纳米孔Al2 O3膜形成新型Si基微结构传感器,利用ANSYS分析软件对微结构进行热分析。采用薄膜工艺、光刻工艺、电化学阳极氧化工艺在Si衬底上制成Si基微结构,采用超声波的方法使聚苯胺敏感材料渗入纳米孔Al2 O3膜中制成气体传感器,并在室温下测试了传感器对氨气的检测特性。结果表明：将纳米孔Al2 O3膜移植到Si基上增加了敏感材料的附着性;传感器对响应时间约为40 s,恢复时间约为960 s,灵敏度随着氨气浓度的增加而增大,并且呈现出良好的线性关系。     

A hybrid chemiresistive sensor system for the detection of organic vapors

A five node sensor array, consisting of three films of gold nanoparticles functionalized with p-terphenylthiol, dodecanethiol and mercapto-(triethylene glycol) methyl ether, and films of poly(3-hexylthiophene) and polypyrrole, was integrated into a portable, microprocessor-based system. The system was evaluated for the detection of chloroform, diisopropyl methylphosphonate (DIMP), ethanol, hexane, methanol, and toluene vapors. Direct comparison of the five sensor films with respect to sensitivity, response time and recovery time was made by measurement of the resistance changes upon simultaneous exposure to each analyte. In general, the sensor films responded, with greatest sensitivity, to organic analyte molecules with similar chemical functionality (e.g., polarity). For example, the dodecanethiol-functionalized gold nanoparticle film sensor excelled at detecting hexane, while the mercapto-(triethylene glycol) methyl ether-functionalized nanoparticle film exhibited superb detection of ethanol and chloroform. Although the poly(3-hexylthiophene) film was very sensitive to polar analytes, including DIMP, in many cases it suffered from relatively long recovery times. Following training of the sensor system, successful differentiation and detection of the analytes were realized using a relatively simple algorithm based on “minimization of the squares of differences” method. The ability of the system to optimally differentiate these analytes is considered within the context of principal component analysis, and the effects of long-term sensor drift are discussed.     

Fabrication of a highly selective Eu(III) membrane sensor based on a new S–N hexadentates Schiff''s base

A novel potentiometric membrane Eu (III) ion sensor is described based on a new S–N hexadentates Schiff's base, bis(thiophenol)butane2,3-dihydrazone (SNSB). The sensor exhibited a Nernstian response over a concentration range of 1.0 × 10⁻⁵ to 1.0 × 10⁻² M, with a detection limit of 5.0 × 10⁻⁶ M. The best performance was achieved with a membrane composition of 30% PVC, 63% o-nitrophenyloctyl ether (NPOE), 5% SNSB, and 5% (0.010 mmol) potassium tetrakis(p-chlorophenyl) borate (KTpClPB). It was found that in the pH range of 3.0–8.5, the potential response of the sensor was not affected by the pH. Furthermore, the electrode presented satisfactory reproducibility, very fast response time (<5 s), and relatively good discriminating ability for Eu(III) ions with respect to many common cations and lanthanide ions, including sodium, potassium, magnesium, calcium, copper, nickel, cobalt, zinc, lead, lanthanum, cerium, gadolinium, samarium, ytterbium, presidium, terbium, neodymium, holmium, erbium, thulium, lutetium, dysprosium, iron and chromium metal ions. The sensor was applied to the determination of fluoride ions in two mouth wash preparations and binary mixtures.     

自适应Kalman滤波修复六维力传感器下E膜模型误差

为减小动载环境下,噪声信号对六维力传感器测量精度的影响,同时解决因传感器的简化模型误差较大,导致标准Kalman滤波无法获取最优估计的问题,提出一种双因子自适应Kalman滤波算法。算法根据正弦激励力响应和应变之间的关系,建立了下E型膜有色噪声增广状态模型。在标准Kalman滤波的基础上,分析了两种模型误差对滤波效果的影响,采用实时调整状态预测在滤波估计中权重的策略,给出了自适应Kalman滤波准则及递推公式。基于正交性原理和最小二乘法准则,利用三段函数模型构造了双重自适应因子。仿真实例表明,与标准Kalman滤波与强跟踪滤波相比,所提算法具有更好的估计精度和稳定性,能够有效地控制模型误差的影响,从而提高六维力传感器的测量精度。     

波段自适应细节注入的高分五号与Sentinel-2遥感影像空谱融合

目的 针对当前空谱融合方法应用到高光谱图像融合时,出现的空间细节信息提升明显但光谱失真,或者光谱保真度高但空间细节信息提升不足的问题,本文提出一种波段自适应细节注入的高分五号（GF-5）高光谱图像（30 m）与Sentinel-2多光谱图像（10 m）的遥感影像空谱融合方法。方法 首先,为了解决两个多波段图像不便于直接融合的问题,提出一种波段自适应的融合策略,对多光谱图像波谱范围以外的高光谱图像波段,以相关系数为标准将待融合图像进行分组。其次,针对传统Gram-Schmidt （GS）融合方法用平均权重系数模拟低分辨率图像造成的光谱失真问题,使用最小均方误差估计计算线性拟合系数,再将拟合图像作为第1分量进行GS正变换,提升融合图像的光谱保真度。最后,为了能同时注入更多的空间细节信息,通过非下采样轮廓波变换将拟合图像、空间细节信息图像和多光谱图像的空间、光谱信息融入到重构的高空间分辨率图像中,再将其与其他GS分量一起进行逆变换,最终得到10 m分辨率的GF-5融合图像。结果 通过与当前用于高光谱图像空谱融合的典型方法比较,本文方法对于受时相影响较小的城镇区域,在提升空间分辨率的同时有较好的光谱保真度,且不会出现噪点;对于受时相变化影响大的植被密集区域,本文方法融合图像有较好的清晰度和地物细节信息,且没有噪点出现。本文方法的CC （correlation coefficient）、ERGAS （erreur relative globale adimensionnelle de synthèse）和SAM （spectral angle mapper）相比于传统GS方法分别提升8%、26%和28%,表明本文方法的光谱保真度大大提高。结论 本文方法的结果空间上没有噪点且光谱曲线与原始光谱曲线基本保持一致,是一种兼具高空间分辨率和高光谱保真度的高光谱图像融合方法。