中性红掺杂SiO2纳米粒子修饰的生物传感器用于大鼠脑渗析液中L-谷氨酸的检测研究

本文以中性红为核，二氧化硅为壳，利用反相微乳液技术，通过正硅酸四乙酯的水解制备了掺杂有中性红的二氧化硅（NR@SiO₂）纳米颗粒。将NR@SiO₂纳米颗粒与_L-谷氨酸氧化酶(GluOx)混合，再通过戊二醛交联修饰于玻碳电极表面，得到以中性红为媒介体的_L-谷氨酸生物传感器。该传感器克服了传统介体型传感器中介体易流失的缺点，而且提高了检测的灵敏度。实验证明，该传感器对_L-谷氨酸的线性检测范围为5.0×10^-7~1.5×10^-4mol/L，检出限为2.0×10^-7 mol/L。与微渗析技术联用，成功地用于检测正常大鼠和患糖尿病大鼠脑中_L-谷氨酸的检测。     

纳米聚苯胺修饰石墨电极的葡萄糖双酶传感器

用循环伏安法在石墨电极上制得纳米纤维聚苯胺, 并在其上固定葡萄糖氧化酶(GOD)和辣根过氧化物酶(HRP)制备葡萄糖双酶传感器. 用交流阻抗、SEM等技术对其进行表征; 考察了各种因素对双酶电极响应电流的影响以及双酶电极的稳定性. 该传感器对葡萄糖响应电流的测定在0.05 V(vs SCE)下进行, 有效避免了电活性物质的影响, 线性响应范围为0.05-2.0 mmol·L-1.     

聚中性红修饰玻碳电极葡萄糖生物传感器

以中性红为电子媒介体,电聚合于Nafion修饰的玻碳电极表面,以戊二醛作交联剂固定葡萄糖氧化酶,最后覆盖一层Nafion膜防止酶流失,构建一种新型葡萄糖生物传感器.详细探讨了传感器的电化学性能及对葡萄糖的最佳响应条件.结果表明,30℃时,传感器在pH 7.0的PBS中对葡萄糖的线性响应范围为1.0×10-5~5.0×10-3mol.L-1.该传感器制作简单、性能优良,有潜在应用前景.     

基于微带阵列电极的微型葡萄糖传感器研究

用微电子薄膜技术制作了微带阵列电极（ＭＡＥ）,考察了该电极在铁氰化钾,过氧化氢溶液中的电化学行为。在微带阵列电极表面,修饰一层全氟代磺酸酯膜作为基底电极,并把电子介体二茂铁及葡萄糖氧化酶固定在基底电极上制备了微型葡萄糖传感器,探讨了微酶电极对葡萄糖氧化过程的催化作用。该微酶电极响应时间小于１０ｓ,检测线性上限为８ｍｍｏｌ／Ｌ。     

聚吡咯修饰乳酸氧化酶电极的研制

根据聚吡咯修饰电极掺杂和去掺杂原理，将乳酸氧化酶固定在玻碳电极表面形成一种新型的乳酸酶电极，该电极灵敏度高，稳定性好，易于制作。本文报道了该电极的研制过程，探讨了影响电极响应的各种因素，找出了最佳实验条件。将此电极用于实际样品中乳酸含量的测定，结果令人满意。     

碳球/钯核壳结构电催化剂的制备和性能研究

分别以葡萄糖、蔗糖、淀粉为碳源,采用水热法制备碳微球;再通过还原法把金属钯负载在碳微球上,制成三种不同的碳球/钯核壳结构电催化剂。采用XRD、SEM、IR对样品的成分、结构和形貌进行分析表征;并将样品制成电极,测试它们的电化学活性。研究结果表明当以淀粉为碳源时,所得碳微球表面羟基官能团丰富,金属钯在该类碳微球上有更好的负载效果,对应的碳球/钯核壳结构电催化剂也表现出更好的电化学活性。对比三类核壳结构电极材料对乙醇和乙二醇的电化学氧化活性表明,三种电极材料对氧化乙二醇有更好的催化活性。     

新型葡萄糖氧化酶电极用于临床血糖的测定

在稳定的普鲁士蓝修饰电极上先涂一酶层 ,然后将二氧化硅溶胶 -凝胶薄膜敷着其上用于固定酶 ,制成了葡萄糖氧化酶电极。采用恒电位安培检测 ,葡萄糖浓度在0.05～4.75mmol/L范围内与响应电流成线性关系 ,检出限为0.02mmol/L ,灵敏度高达1.182μA·mmol -1·L ,响应时间为12s ;该酶电极不受抗坏血酸、尿酸等电活性物质的干扰 ,稳定性较好。该电极用于临床血糖的测定 ,回收率为96 %～110 % ,测定结果与酶偶联比色法结果一致 ,可用于临床糖尿病人血糖的检测。     

手性聚苯胺/二氧化硅核/壳复合物的合成及应用

以苯胺为单体,右旋樟脑磺酸为手性掺杂剂制备了手性聚苯胺[(+)-PANI];以(+)-PANI为核,表面包覆二氧化硅外壳,得到手性聚苯胺/二氧化硅核/壳复合物[(+)-PANI@SiO_2].采用比旋度([α]t D)、紫外-可见光谱(UV-Vis)及圆二色谱(CD)等表征光学活性,结果表明,(+)-PANI及(+)-PANI@SiO_2均具有手性;红外光谱(IR)表明,二氧化硅已经包覆于(+)-PANI表面;扫描电子显微镜(SEM)结果表明,(+)-PANI@SiO_2为核/壳结构.将(+)-PANI和(+)-PANI@SiO_2分别用于丙氨酸对映体选择性结晶,L-丙氨酸均优先结晶,且(+)-PANI@SiO_2手性识别能力更强.以光学活性聚苯胺为核,无机二氧化硅为壳的核/壳复合物在手性识别领域具有潜在的应用价值.     

基于表面重建螺旋型铂铱电极的葡萄糖生物传感器

通过对螺旋型铂铱电极表面进行化学腐蚀和电化学沉积铂纳米粒子实现电极表面的重建和优化,研究了螺旋型铂铱电极在不同腐蚀时间和电沉积时间下的形貌及对过氧化氢(H2O2)的催化活性.对表面重建的工作电极涂覆氧化酶和半透膜,制备出了铂纳米粒子/葡萄糖氧化酶/环氧聚氨酯酶电极,并将其用作葡萄糖传感器的工作电极.传感器计时电流检测结果表明,表面重建后的酶电极传感器对葡萄糖的检测范围扩大为2~45 mmol/L,优于裸铂铱酶电极传感器,电流响应值和灵敏度得到明显提升,同时传感器还具有良好的稳定性和选择性.     

以Nafion修饰的镀铂玻碳电极为基底的半乳糖传感器的制备

在镀铂的玻碳电极表面,修饰一层全氟代磺酸酯(Nafion)膜,制成基底电极。用化学交联法将半乳糖氧化酶(GAD)固定在基底电极表面,即制成半乳糖传感器。和光亮铂相比,镀铂电极对过氧化氢有更高的响应,而Nafion膜可以消除抗坏血酸,尿酸等电活性物质对测定的影响,提高了酶电极测定的选择性。D-半乳糖测定的线性范围为0.25～4.25 mmol/L,响应时间小于30s。电极连续使用300次,没有明显的电流变化。该电极具有快速、准确,选择性高的特点。     

Simultaneous assay of glucose,lactate, <Emphasis Type="SmallCaps">L</Emphasis>-glutamate and hypoxanthine levels in a rat striatum using enzyme electrodes based on neutral red-doped silica nanoparticles

An electrochemical method suitable for the simultaneous measurement of cerebral glucose, lactate, L-glutamate and hypoxanthine concentrations from in vivo microdialysis sampling has been successfully performed for the first time using a neutral red-doped silica (NRDS) nanoparticle-derived enzyme sensor system. These uniform NRDS nanoparticles (about 50±3 nm) were prepared by a water-in-oil (W/O) microemulsion method, and characterized by a TEM technique. The neutral red-doped interior maintained its high electron-activity, while the exterior nano-silica surface prevented the mediator from leaching out into the aqueous solution, and showed high biocompability. These nanoparticles were then mixing with the glucose oxidase (GOD), lactate oxidase (LOD), L-glutamate oxidase (L-GLOD) or xanthine oxidase (XOD), and immobilized on four glassy carbon electrodes, respectively. A thin Nafion film was coated on the enzyme layer to prevent interference from molecules such as ascorbic acid and uric acid in the dialysate. The high sensitivity of the NRDS modified enzyme electrode system enables the simultaneous monitoring of trace levels of glucose, L-glutamate, lactate and hypoxanthine in diluted dialysate samples from a rat striatum.     

Bicomponent Microneedle Array Biosensor for Minimally‐Invasive Glutamate Monitoring

This article describes the design of a new and attractive minimally‐invasive bicomponent microneedle sensing device for the electrochemical monitoring of the excitatory neurotransmitter glutamate and glucose. The new device architecture relies on the close integration of solid and hollow microneedles into a single biosensor array device containing multiple microcavities. Such microcavities facilitate the electropolymeric entrapment of the recognition enzyme within each microrecess. The resulting microneedle biosensor array can be employed as a minimally‐invasive on‐body transdermal patch, obviating the extraction/sampling of the biological fluid, thereby simplifying device requirements. The new concept is demonstrated for the electropolymeric entrapment of glutamate oxidase and glucose oxidase within a poly(o‐phenylenediamine) (PPD) thin film. The PPD‐based enzyme entrapment methodology enables the effective rejection of coexisting electroactive interferents without compromising the sensitivity or response time of the device. The resulting microneedle‐based glutamate and glucose biosensors thus exhibit high selectivity, sensitivity, speed, and stability in both buffer and undiluted human serum. High‐fidelity glutamate measurements down to the 10 µM level are obtained in serum. The attractive recess design also serves to protect the enzyme layer upon insertion into the skin. This simple, yet robust microneedle design is well‐suited for diverse biosensing applications in which real‐time metabolite monitoring is a core requirement.     

Development of an Amperometric Biosensor for β‐N‐Oxalyl‐L‐α,β‐Diaminopropionic Acid (β‐ODAP)

An amperometric method for the determination of the neurotoxic amino acid β‐N‐oxalyl‐L ‐α,β‐diaminopropionic acid (β‐ODAP) using a screen printed carbon electrode (SPCE) is reported. The electrode material was bulk‐modified with manganese dioxide and used as a detector in flow injection analysis (FIA). The enzyme glutamate oxidase (GlOx) was immobilized in a Nafion‐film on the electrode surface. The performance of the biosensor was optimized using glutamate as an analyte. Optimum parameters were found as: operational potential 440 mV (vs. Ag/AgCl), flow rate 0.2 mL min^?1, and carrier composition 0.1 mol L^?1 phosphate buffer (pH 7.75). The same conditions were used for the determination of β‐ODAP. The signal was linear within the concentration range 53–855 μmol L^?1 glutamate and 195–1950 μmol L^?1 β‐ODAP. Detection limits (as 3σ value) for both analytes were 9.12 and 111.0 μmol L^?1, respectively, with corresponding relative standard deviations of 3.3 and 4.5%. The biosensor retained more than 73% of its activity after 40 days of on‐line use.     

Amperometric Glucose Biosensor Based on Rhodium Dioxide‐Modified Carbon Ink

An amperometric method for the determination of glucose using a screen printed carbon electrode is reported. The electrode material was bulk modified with rhodium dioxide and the enzyme glucose oxidase immobilized in a Nafion‐film on the electrode surface and investigated for its ability to serve as a detector of glucose in flow injection analysis. The sensor exhibited a linear increase of the amperometric signal with the concentration of glucose in the range of 1–250 mg L^?1 with a detection limit (evaluated as 3σ) of 0.2 mg L^?1 under optimized flow rate of 0.4 mL min^?1 in 0.1 M phosphate buffer (pH 7.5) carrier. At the potential applied (?0.2 V vs. Ag/AgCl), interferences from redox species present in the sample matrix were negligible. The biosensor reported here retained its activity for more than 40 injections or 4 months of storage at 6 °C. The RSD was determined as 1.8% for a glucose concentration of 25 mg L^?1 (n=5) with a typical response time of about 28 s.     

Minimally‐invasive Microneedle‐based Biosensor Array for Simultaneous Lactate and Glucose Monitoring in Artificial Interstitial Fluid

Here we report the first mediated pain free microneedle‐based biosensor array for the continuous and simultaneous monitoring of lactate and glucose in artificial interstitial fluid (ISF). The gold surface of the microneedles has been modified by electrodeposition of Au‐multiwalled carbon nanotubes (MWCNTs) and successively by electropolymerization of the redox mediator, methylene blue (MB). Functionalization of the Au‐MWCNTs/polyMB platform with the lactate oxidase (LOX) enzyme (working electrode 1) and with the FAD‐Glucose dehydrogenase (FADGDH) enzyme (working electrode 2) enabled the continuous monitoring of lactate and glucose in the artificial ISF. The lactate biosensor exhibited a high sensitivity (797.4±38.1 μA cm^?2 mM^?1), a good linear range (10–100 μM) with a detection limit of 3 μM. The performance of the glucose biosensor were also good with a sensitivity of 405.2±24.1 μA cm^?2 mM^?1, a linear range between 0.05 and 5 mM and a detection limit of 7 μM. The biosensor array was tested to detect the amount of lactate generated after 100 minutes of cycling exercise (12 mM) and of glucose after a normal meal for a healthy patient (10 mM). The results reveal that the new microneedles‐based biosensor array seems to be a promising tool for the development of real‐time wearable devices with a variety of sport medicine and clinical care applications.     

A Nanocomposite Chitosan Based on Ferrocene‐Modified Silica Nanoparticles and Carbon Nanotubes for Biosensor Application

A novel amperometric biosensor for glucose was developed by entrapping glucose oxidase (GOD) in a chitosan composite doped with ferrocene monocarboxylic acid‐aminated silica nanoparticles conjugate (FMC‐ASNPs) and multiwall carbon nanotubes (MWNTs). The entrapped FMC‐ASNPs conjugate performed excellent redox electrochemistry and the presence of MWNTs improved the conductivity of the composite film. This matrix showed a biocompatible microenvironment for retaining the native activity of the entrapped GOD and was in favor of the accessibility of substrate to the active site of GOD, thus the affinity to substrates is improved greatly. Under optimal conditions this biosensor was able to detect glucose with a detection limit of 10 μM (S/N=3) in the linear range of 0.04 to 6.5 mM. The proximity of these three components FMC‐ASNPs, MWNTs and GOD enhanced the electron transfer between the film and electrode. This composite film can be extended to immobilize other enzymes and biomolecules, which will greatly facilitate the development of biosensors and other bioelectrochemical devices.     

Magnetite NPs@C with Highly‐Efficient Peroxidase‐Like Catalytic Activity as an Improved Biosensing Strategy for Selective Glucose Detection

This work reports the novel application of carbon‐coated magnetite nanoparticles (mNPs@C) as catalytic nanomaterial included in a composite electrode material (mNPs@C/CPE) taking advantages of their intrinsic peroxidase‐like activity. The nanostructured electrochemical transducer reveals an enhancement of the charge transfer for redox processes involving hydrogen peroxide. Likewise, mNPs@C/CPE demonstrated to be highly selective even at elevated concentrations of ascorbic acid and uric acid, the usual interferents of blood glucose analysis. Upon these remarkable results, the composite matrix was further modified by the addition of glucose oxidase as biocatalyst, in order to obtain a biosensing strategy (GOx/mNPs@C/CPE) with enhanced properties for the electrochemical detection of glucose. GOx/mNPs@C/CPE exhibit a linear range up to 7.5×10^?3 mol L^?1 glucose, comprising the entirely physiological range and incipient pathological values. The average sensitivity obtained at ?0.100 V was (1.62±0.05)×10⁵ nA L mol^?1 (R²=0.9992), the detection limit was 2.0×10^?6 M while the quantification limit was 6.1×10^?6 mol L^?1. The nanostructured biosensor demonstrated to have an excellent performance for glucose detection in human blood serum even for pathological values.     

Electrogenerated Chemiluminescence of Tris(2,2′‐bipyridyl)ruthenium(II) Immobilized in Humic Acid‐Silica‐Poly(vinyl alcohol) Composite Films

In this paper, we report the first attempt to use humic acid (HA) as modifiers to prepare the organic‐inorganic hybrid modified glassy carbon electrodes based on HA‐silica‐PVA (poly(vinyl alcohol)) sol‐gel composite. Electroactive species of tris(2,2′‐bipyridyl)ruthenium(II) (Ru(bpy) ) can easily incorporate into the HA‐silica‐PVA films to form Ru(bpy) modified electrodes. The amount of Ru(bpy) incorporated in the composite films strongly depends on the amount of HA in the hybrid sol. Electrochemical and electrogenerated chemiluminescence (ECL) of Ru(bpy) immobilized in HA‐silica composite films coated on a glassy carbon electrode have been studied with tripropylamine (TPA) as the coreactant. The analytical performance of this modified electrode was evaluated in a flow injection analysis (FIA) system with a homemade flow cell. The as‐prepared electrode showed good stability and high sensitivity. The detection limits (S/N=3) were 0.050 μmol L^?1 for TPA and 0.20 μmol L^?1 for oxalate, and the linear ranges were from 0.10 μmol L^?1 to 1.0 mmol L^?1 for TPA and from 1.0 μmol L^?1 to 1.0 mmol L^?1 for oxalate, respectively. The resulting electrodes were stable over two months.     

Amino‐Containing Ultrafine Organosilica‐Nanoparticle‐Modified Au Electrode for the Determination of Cu(II) Ions

Using 3‐Aminopropyltriethoxysilane(APTES) as a single silica source, an amino‐rich ultrafine organosilica‐nanoparticle‐modified Au electrode was fabricated, following the formation of (3‐mercaptopropyl)‐trimethoxysilane (MPTS) monolayer on Au surface (MPTS/Au). With cetyltrimethylammonium bromide as an additive, APTES‐based gel particles on the electrode have a narrow particle size distribution of 4–7 nm and “crystal‐like” structure. AFM and electrochemical characterization confirmed the successful grafting of APTES nanoparticles on MPTS/Au. The APTES/MPTS/Au electrode is highly sensitive for the detection of copper(II) ions with a detection limit as low as 1.6×10^?12 mol L^?1 (S/N>3) by square wave voltammetry. The current is linear to copper(II) concentration between 1.6×10^?12 and 6.25×10^?10 mol L^?1.     

Silica/Poly(1,5‐dioxepan‐2‐one) Hybrid Nanoparticles by “Direct” Surface‐Initiated Polymerization

Summary: Biodegradable poly(1,5‐dioxepan‐2‐one) (PDXO) was grown directly from Si OH groups of a silica nanoparticle by surface‐initiated, ring‐opening polymerization (SI‐ROP) of 1,5‐dioxepan‐2‐one (DXO). The direct SI‐ROP of DXO was achieved by heating a mixture of Sn(Oct)₂, DXO, and the silica nanoparticles (316 nm in diameter) in anhydrous toluene. The resulting silica/PDXO hybrid nanoparticles were characterized by means of ¹H NMR spectroscopy, IR spectroscopy, thermogravimetric analysis, and field‐emission scanning electron microscopy.

The procedure for the surface‐initiated, ring‐opening polymerization of 1,5‐dioxepan‐2‐one on silica nanoparticles reported here.