A chiral,porous, organic cage‐based,enantioselective potentiometric sensor for 2‐aminobutanol

A new enantioselective potentiometric sensor containing R‐type chiral porous organic cage CC9 as the chiral selector was designed for the assay of 2‐aminobutanol. Optimized membrane electrodes displayed a linear dynamic range from 10⁻³ ~ 10⁻¹ mol·L⁻¹ with a detection limit of 2.5 × 10⁻⁴ mol·L⁻¹ and a Nernstian response of 27 ± 0.5mV·decade⁻¹ toward S‐2‐aminobutanol within the pH range 7.0–10.0. The potentiometric enantioselectivity coefficient ( ) of this sensor was −1.333, indicating that the porous organic cage‐based electrode exhibited good discrimination toward S‐2‐aminobutanol over R‐2‐aminobutanol.     

An ultrasensitive electrochemiluminescent sensor based on a pencil graphite electrode modified with CdS nanorods for detection of chlorogenic acid in honeysuckle

In this paper, a novel and ultrasensitive electrochemiluminescent sensor employing a solvothermal‐synthesized CdS nanorod‐modified pencil graphite electrode (CdS/PGE) for the determination of chlorogenic acid (CA) is fabricated. In the first step, the PGE surface is modified using CdS nanorods. In the next step, the developed electrode is used to detect CA using a electrochemiluminescent (ECL) technique, in which potassium persulfate (K₂S₂O₈) served as a co‐reactant. The possible ECL mechanism is investigated, and the influences of pH and cyclic voltammetric scanning rate on the signal response are studied. The ECL intensity decreases quantitatively in relation to the concentration of the target molecule. Under optimized conditions, the linear correlation between the quenched ECL intensity and the logarithm of CA concentration is observed in the range from 2 × 10^?9 to 8 × 10^?7 mol L^?1 with a limit of detection of 1 × 10^?9 mol L^?1. This proposed method is applied to the analysis of CA in honeysuckle flower, giving recoveries of 99‐107%. The experimental results demonstrate that this ECL sensor shows good stability and reproducibility.     

Molecularly imprinted electrochemiluminescence sensor based on ZIF-8 doped with CdSe quantum dots for the detection of trace estriol

A composite of the metal–organic framework compound ZIF-8 doped with CdSe quantum dots (QDs) with sensitive and stable luminescence was synthesized, and a molecularly imprinted electrochemiluminescence (ECL) sensor was constructed based on this composite. The ZIF-8@CdSe molecularly imprinted ECL sensor combines the high sensitivity of ECL and the high selectivity of molecular imprinting to realize the sensitive and specific detection of estriol. CdSe QDs and gold nanoparticles were encapsulated within ZIF-8 to obtain the ZIF-8@CdSe QDs/GNP (ZIF@CdSe/GNP) composite. Subsequently, the GNPs were further loaded on the surface of this composite to obtain the GNP/ZIF@CdSe/GNP composite. l -Cysteine was used to immobilize the GNP/ZIF@CdSe/GNP composite on the surface of a gold electrode to obtain the GNP/ZIF@CdSe/GNP-modified gold electrode. A molecularly imprinted polymer (MIP) film was prepared on the surface of the modified electrode by electropolymerization with o-phenylenediamine as the functional monomer and estriol as the template molecule. After elution, estriol could be specifically recognized by the cavities. The readsorption of estriol by the MIP can prevent the coreactant from reaching the electrode surface through the cavities, thereby weakening ECL. A good linear relationship existed between the ∆ECL and lg C of estriol concentrations of 1 × 10⁻¹⁴ to 1 × 10⁻⁹ mol·L⁻¹. The detection limit was as low as 8.9 × 10⁻¹⁶ mol·L⁻¹. The sensor was applied in the determination of estriol in serum samples with a recovery of 97.0–102%.     

Electrogenerated chemiluminescence of ruthenium complex immobilized in a highly cross‐linked polymer and its analytical applications

Electrogenerated chemiluminescence (ECL) of a ruthenium complex polymer modified carbon paste electrode and its analytical applications were investigated. The ruthenium complex polymer was prepared using bis(2,2‐bipyridine) (4,4‐dicarboxy‐2,2‐bipyridine) ruthenium(II). The ECL behaviours of ruthenium complex polymer modified carbon paste electrode were investigated in the absence and presence of tripropylamine (TPA). The modified carbon paste electrode exhibited long‐term stability and fine reproducibility. The ECL intensity of the modified carbon paste electrode was linear with the concentration of TPA in the range 2.0 × 10^–6–3.8 × 10^–3 mol/L, with a detection limit (S:N = 3) of 6 × 10^–7 mol/L. It was also found that raceanisodamine could enhance the ECL intensity of the modified electrode. The ECL intensity of the modified carbon paste electrode was linear with the concentration of raceanisodamine in the range 1.1 × 10^–5–6.0 × 10^–4 mol/L, with a detection limit (S:N = 3) of 6 × 10^–6 mol/L. This work demonstrates that the entrapment of ruthenium complex in a highly cross‐linked polymer is a promising approach to construct an ECL modified electrode with long‐term stability and fine reproducibility. The modified electrode designed has a potential application in the ECL detector. Copyright © 2008 John Wiley & Sons, Ltd.     

Overoxidized polypyrrole/multi-walled carbon nanotubes composite modified electrode for in vivo liquid chromatography–electrochemical detection of dopamine

Overoxidized polypyrrole/multi-walled carbon nanotubes (OPPy/MWNTs) modified electrode has been developed for sensitively detecting dopamine (DA). OPPy films developed outside MWNTs might have a porous morphology. Thus, OPPy/MWNTs films developed by this method do not reject ascorbic acid (AA). However, OPPy/MWNTs modified electrode shows largely enhancing oxidative current responses of DA. When combined with liquid chromatography, it not only obtains a low detection limit of 7.5 × 10^?10 mol L^?1 for DA, but also improves the selectivity of DA detection. Mechanisms for the enhancement are also well discussed in this paper. With this approach, microdialysis has been employed for successful assessment of DA in rat striatum.     

Eco‐friendly synthesis of gelatin‐capped bimetallic Au–Ag nanoparticles for chemiluminescence detection of anticancer raloxifene hydrochloride

This study described the utility of green analytical chemistry in the synthesis of gelatin‐capped silver, gold and bimetallic gold–silver nanoparticles (NPs). The preparation of nanoparticles was based on the reaction of silver nitrate or chlorauric acid with a 1.0 wt% aqueous gelatin solution at 50°C. The gelatin‐capped silver, gold and bimetallic NPs were characterized using transmission electron microscopy, UV–vis, X‐ray diffraction and Fourier transform infrared spectroscopy, and were used to enhance a sensitive sequential injection chemiluminescence luminol–potassium ferricyanide system for determination of the anticancer drug raloxifene hydrochloride. The developed method is eco‐friendly and sensitive for chemiluminescence detection of the selected drug in its bulk powder, pharmaceutical injections and biosamples. After optimizing the conditions, a linear relationship in the range of 1.0 × 10^–9 to 1.0 × 10^–1 mol/L was obtained with a limit of detection of 5.0 × 10^–10 mol/L and a limit of quantification of 1.0 × 10^‐9 mol/L. Statistical treatment and method validation were performed based on ICH guidelines. Copyright © 2016 John Wiley & Sons, Ltd.     

Enhanced electrochemiluminescence from reduced graphene oxide–CdTe quantum dots for highly selective determination of copper ion

An electrochemiluminescence (ECL) sensor based on reduced graphene oxide–CdTe quantum dots (RGO–CdTe QDs) composites for detecting copper ion (Cu²⁺) was proposed. The ECL behaviours of the RGO–CdTe QD modified electrode were investigated with H₂O₂ as the co‐reactant. Quantitative detection of Cu²⁺ was realized as Cu²⁺ could effectively quench the ECL signal of the RGO–CdTe QDs. A wide linear range of 1.00 × 10^?14 to 1.00 × 10^?4 M (R = 0.9953) was obtained under optimized conditions, and a detection limit (S/N = 3) was achieved of as low as 3.33 × 10^?15 M. The proposed sensor also exhibited good stability and selectivity for the detection of copper ions. Finally, the analytical application of the proposed sensor was also evaluated using river water.     

Electrochemiluminescence detection of methamphetamine based on a Ru(bpy)32+‐doped silica nanoparticles/Nafion composite film modified electrode

An electrochemiluminescence (ECL) approach for methamphetamine determination was developed based on a glassy carbon electrode modified with a Ru(bpy)₃²⁺‐doped silica nanoparticles/Nafion composite film. The monodispersed nanoparticles, which were about 50 nm in size, were synthesized using the water‐in‐oil microemulsion method. The ECL results revealed that Ru(bpy)₃²⁺ doped in silica nanoparticles retained its original photo‐ and electrochemical properties. The ECL intensity was found to be proportional to methamphetamine concentration over the range from 1.0 × 10^?7 to 1.0 × 10^?5 mol L^?1, and the detection limit was found to be 2.6 × 10^?8 mol L^?1. The proposed ECL approach was used to analyze the methamphetamine content in drugs. Copyright © 2009 John Wiley & Sons, Ltd.     

A Visualized Assay for Quercetin Based on the Formation of Silver–Gold Alloy Nanoparticles

A visualized assay for quercetin (QU) was first developed based on the formation of silver–gold alloy nanoparticles in this contribution. With the ability to reduce metal ions to metal substances, QU could reduce Ag⁺ absorbed on the surface of gold nanoparticles to metallic silver. The thickness of the formed Ag shell and the color change of the solution were proportional to the concentration of QU. Therefore, visualized detection of QU could be realized by studying the surface resonance plasmon absorption spectra of the analytical systems after addition of different concentration of QU. Under optimum conditions, trace amount of QU could be detected in the linear range 9.0?×?10^?7–1.0?×?10^?4 mol L^?1 with a detection limit of 6.5?×?10^?7 mol L^?1. The present assay was applied in the determination of QU in human serum and satisfactory results were obtained. This assay is simple, rapid, and cost-effective, and it is a powerful complement for the spectroscopy assays for QU. Also, it is the first visualized spectroscopic assay of QU until now.     

The effects of copper on photosynthesis and biomolecules yield in Chlorolobion braunii

Our knowledge of the effects of copper on microalgal physiology is largely based on studies conducted with high copper concentrations; much less is known when environmentally relevant copper levels come into question. Here, we evaluated the physiology of Chlorolobion braunii exposed to free copper ion concentrations between 5.7 × 10^?9 and 5.0 × 10^?6 mol · L^?1, thus including environmentally relevant values. Population growth and maximum photosynthetic quantum yield of PSII were determined daily during the 96 h laboratory controlled experiment. Exponentially‐growing cells (48 h) were analyzed for effective quantum yield and rapid light curves (RLC), and total lipids, proteins, carbohydrates, chlorophyll a and carotenoids were determined. The results showed that growth rates and population density decreased gradually as copper increased in experiment, but the photosynthetic parameters (maximum and effective quantum yields) and photochemical quenching (qP) decreased only at the highest free copper concentration tested (5.0 × 10^?6 mol · L^?1); nonphotochemical quenching (NPQ) increased gradually with copper increase. The RLC parameters Ek and rETRmax were inversely proportional to copper concentration, while α and Im decreased only at 5.0 × 10^?6 mol · L^?1. The effects of copper in biomolecules yield (mg · L^?1) varied depending on the biomolecule. Lipid yield increased at free copper concentration as low as 2.5 × 10^?8 mol · L^?1, but proteins and carbohydrates were constant throughout.     

Determination of pholcodine in syrups and human plasma using the chemiluminescence system of tris(1,10 phenanthroline)ruthenium(II) and acidic Ce(IV)

Pholcodine is an opiate derivative drug which is widely used in pediatric medicine. In this study, a chemiluminescence (CL) method is described that determines pholcodine in human plasma and syrup samples. This method is based on the fact that pholcodine can greatly enhance the weak CL emission of reaction between tris(1,10 phenanthroline)ruthenium(II), Ru(phen)₃²⁺, and acidic Ce(IV). The CL mechanism is described in detail using UV–vis light, fluorescence and CL spectra. Effects of chemical variables were investigated and under optimum conditions, CL intensity was proportional to the pholcodine concentration over the range 4.0 × 10^?8 to 8.0 × 10^?6 mol  L^?1. The limit of detection (LOD) (S/N = 3) was 2.5 × 10^?8 mol  L^?1. Percent of relative standard deviations (%RSD) for 3.0 × 10^?7 and 3.0 × 10^?6 mol  L^?1 of pholcodine was 2.9 and 4.0%, respectively. Effects of common ingredients were investigated and the method was applied successfully to the determination of pholcodine in syrup samples and human plasma.     

CdS nanoparticles‐ enhanced chemiluminescence and determination of baicalin in pharmaceutical preparations

CdS nanoparticles (CdS NPs) of different sizes were synthesized by the citrate reduction method. It was found that CdS NPs could enhance the chemiluminescence (CL) of the luminol‐potassium ferricyanide system and baicalin could inhibit CdS NPs‐enhanced luminol‐potassium ferricyanide CL signals in alkaline solution. Based on this inhibition, a flow‐injection CL method was established for determination of baicalin in pharmaceutical preparations and human urine samples. Under optimized conditions, the linear range for determination of baicalin was 5.0 x 10^?6 to 1.0 x 10^?3 g/L. The detection limit at a signal‐to‐noise ratio of 3 was 1.7 x 10 ^?6 g/L. CL spectra, UV‐visible spectra and transmission electron microscopy (TEM) were used to investigate the CL mechanism. The method described is simple, selective and obviates the need of extensive sample pretreatment. Copyright © 2012 John Wiley & Sons, Ltd.     

Hydrogen peroxide sensor based on Prussian blue electrodeposited on (3-mercaptopropyl)-trimethoxysilane polymer-modified gold electrode

A hydrogen peroxide (H₂O₂) sensor was developed by electrodepositing Prussian blue (PB) on a gold electrode modified with (3-mercaptopropyl)-trimethoxysilane (MPS) polymer. The characterization of the self-assembled electrode was investigated by cyclic voltammetry and electrochemical impedance spectroscopy. The results of electrochemical experiments showed that such constructed sensor had a favorable catalytic ability to reduce H₂O₂. The MPS film on the modified gold electrode greatly enhanced the pH-adaptive range of PB. Large surface-to-volume ratio property of double-layer 2d-network MPS-modified PB electrode enabled stable and highly sensitive performance of the non-enzymatic H₂O₂ sensor. The linear range of H₂O₂ determined is from 2.0 × 10⁻⁶ to 2.0 × 10⁻⁴ mol L⁻¹ with a correlation coefficient of 0.9991 and a detection limit for H₂O₂ of 1.8 × 10⁻⁶ mol L⁻¹. The influences of the potentially interfering substances on the determination of H₂O₂ were investigated. This modified electrode exhibits a good selectivity and high sensitivity with satisfactory results.     

A hydrogen peroxide biosensor based on the direct electrochemistry of hemoglobin modified with quantum dots

Direct electron transfer of hemoglobin modified with quantum dots (QDs) (CdS) has been performed at a normal graphite electrode. The response current is linearly dependent on the scan rate, indicating the direct electrochemistry of hemoglobin in that case is a surface-controlled electrode process. UV–vis spectra suggest that the conformation of hemoglobin modified with CdS is little different from that of hemoglobin alone, and the conformation changes reversibly in the pH range 3.0–10.0. The hemoglobin in a QD film can retain its bioactivity and the modified electrode can work as a hydrogen peroxide biosensor because of its peroxidase-like activity. This biosensor shows an excellent response to the reduction of H₂O₂ without the aid of an electron mediator. The catalytic current shows a linear dependence on the concentration of H₂O₂ in the range 5 × 10⁻⁷–3 × 10⁻⁴ M with a detection limit of 6 × 10⁻⁸ M. The response shows Michaelis–Menten behavior at higher H₂O₂ concentrations and the apparent Michaelis–Menten constant is estimated to be 112 μM.     

Flow‐injection chemiluminescence of the luminol–potassium periodate system enhanced by TGA–capped CdTe quantum dots for the determination of theophylline

The chemiluminescence (CL) behaviour of the luminol–potassium periodate system enhanced by CdTe quantum dots capped with thioglycolic acid (TGA–CdTe QDs) was studied using kinetic experiments, CL spectra, UV–vis absorption spectra and fluorescence spectra. The production of oxygen‐containing reactant intermediates (O₂^?? and OH^?) in the present CL system was verified by CL. The possible CL mechanism was discussed in detail. Furthermore, theophylline (THP) was determined based on its enhancement of the CL intensity of the CdTe QDs–luminol–potassium periodate system coupled with a flow‐injection technique. Under these optimized conditions, the linear range was found to be from 1.0 × 10^?8 to 1.0 × 10^?5 g/mL with a detection limit of 2.8 × 10^?9 g/mL (3σ). The recoveries for the determination of THP in tablets were from 98.2 to 99.6%.     

流动注射化学发光法检测剑麻皂苷元

采用Luminol-K3Fe(CN)6化学发光体系,建立流动注射化学发光法检测从剑麻残渣和麻膏中分离得到的皂苷元。当用0.1 mol·L-1NaOH作为溶剂配制鲁米诺浓度为1.0×10-5mol·L-1,用去离子水作为溶剂配制K3Fe(CN)6浓度为1.6×10-5mol·L-1,主副蠕动泵转数均在50~80 r·min-1时,用无水乙醇溶解的皂苷元流入体系具有最强的化学发光。在该条件下,剑麻皂苷元最低检出限为3.0×10-3mg·mL-1,标准曲线相关系数为0.999 6,平均回收率为98.5%,相对标准偏差在2.9%~4.2%之间。同时与HPLC检测方法对样品检测结果进行了比较。     

A biosensor based on gold nanoparticles,dihexadecylphosphate, and tyrosinase for the determination of catechol in natural water

In this work, a biosensor using a glassy carbon electrode modified with gold nanoparticles (AuNPs) and tyrosinase (Tyr) within a dihexadecylphosphate film is proposed. Cystamine and glutaraldehyde crosslinking agents were used as a support for Tyr immobilization. The proposed biosensor was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and cyclic voltammetry in the presence of catechol. The determination of catechol was carried out by amperometry and presented a linear concentration range from 2.5 × 10⁻⁶ to 9.5 × 10⁻⁵ mol L⁻¹ with a detection limit of 1.7 × 10⁻⁷ mol L⁻¹. The developed biosensor showed good repeatability and stability. Moreover, this novel amperometric method was successfully applied in the determination of catechol in natural water samples. The results were in agreement with a 95% confidence level for those obtained using the official spectrophotometric method.     

Nuclear fast red‐based colorimetric sensors for sensitive and selective detection of Ag ions

The reduction of nuclear fast red (NFR) stain by sodium tetrahydroboron was catalyzed in the presence of silver ions (Ag⁺). The fluorescence properties of reduced NFR differed from that of NFR. The product showed fluorescence emission at 480 nm with excitation at 369 nm. Furthermore, the fluorescence intensity of the mixture increased strongly in the presence of Ag⁺ and Britton–Robinson buffer at pH 4.78. There was a good linear relationship between increased fluorescence intensity (ΔI) and Ag⁺ concentration in the range 5.0 × 10^?9 to 5.0 × 10^?8 M. The correlation coefficient was 0.998, and the detection limit (3σ/k) was 1.5 × 10^?9 M. The colour of the reaction system changed with variation in Ag⁺ concentration over a wide range. Based on the colour change, a visual semiquantitative detection method for recognition and sensing of Ag⁺ was developed for the range 1.0 × 10^?8 to 5.0 × 10^?4 M, with an indicator that was visible to the naked eye. Therefore, a sensitive, simple method for determination of Ag⁺ was developed. Optimum conditions for Ag⁺ detection, the effect of other ions and the analytical application of Ag⁺ detection of synthesized sample were investigated.     

Enhanced Efficiency of In Vitro Rootstock Micro-propagation Using Silica-Based Nanoparticles and Plant Growth Regulators in Myrobalan 29C (Prunus cerasifera L.)

Different experiments were conducted to establish and optimize an efficient in vitro micropropagation protocol for Myrobalan 29C rootstocks. Disinfection of initial explants with AgNPs (2.5%) reduced the needed amount of NaClO (5.0%) by half. The highest rates of induced active buds were obtained in the DKW (90.63%), MS (86.67%), modified MS (82.22%), and WPM (78.15%) culture media supplemented with BAP (2.22 μmol L^?1)?+?GA₃ (2.88 μmol L^?1)?+?IBA (0.05 μmol L^?1)?+?Fe-EDDHA (228.72 μmol L^?1). The highest quality of the proliferated shoots (5.0) was also achieved using DKW medium. Inclusion of GA₃ (5.76 μmol L^?1), Fe-EDDHA (114.36–228.72 μmol L^?1), or BAP (2.22 μmol L^?1) were also able to enhance the rate of shoot multiplication. Compared to the agar-solidified culture system, the established shoots proliferated more efficiently when immersed by bioreactor in the liquid DKW culture medium on a regular basis. Exogenous application of silica-based nanoparticles (NPs) including the chemically synthesized silica NPs (TSiO₂ NPs, 1.0 ppm), rice husk derived biogenic silica NPs (RSiO₂ NPs, 10.0 ppm), or amine modified silica NPs (ASiO₂ NPs, 10.0 ppm) to the multiplication medium increased the number of regenerated lateral shoots by 520%, 360%, and 349%, respectively. Proliferated shoots with well-developed root system were obtained from the rooting medium supplemented with 19.68 μmol L^?1 IBA. Our results indicated that the rootstocks of Myrobalan 29C could be efficiently propagated under in vitro condition providing proper culture medium and optimal concentrations of additives and plant growth regulators were adopted.

     

Determination of pioglitazone hydrochloride by flow injection chemiluminescence tris(2,2′-bipyridyl)ruthenium(II)–silver(III) complex system

A novel flow injection-chemiluminescence (FI–CL) approach is proposed for the assay of pioglitazone hydrochloride (PG-HCl) based on its enhancing influence on the tris(2,2′-bipyridyl)ruthenium(II)–silver(III) complex (Ru(bipy)₃²⁺-DPA) CL system in sulfuric acid medium. The possible CL reaction mechanism is discussed with CL and ultraviolet (UV) spectra. The optimum experimental conditions were found as: Ru(bipy)₃²⁺, 5.0 × 10⁻⁵ M; sulfuric acid, 1.0 × 10⁻³ M; diperiodatoargentate(III) (DPA), 1.0 × 10⁻⁴ M; potassium hydroxide, 1.0 × 10⁻³ M; flow rate 4.0 ml min⁻¹ for each flow stream and sample loop volume, 180 μl. The CL intensity of PG-HCl was linear in the range of 1.0 × 10⁻³ to 5.0 mg L⁻¹ (R² = 0.9998, n = 10) with limit of detection [LOD, signal-to-noise ratio (S/N) = 3] of 2.2 × 10⁻⁴ mg L⁻¹, limit of quantification (LOQ, S/N = 10) of 6.7 × 10⁻⁴ mg L⁻¹, relative standard deviation (RSD) of 1.0 to 3.3% and sampling rate of 106 h⁻¹. The methodology was satisfactorily used to quantify PG-HCl in pharmaceutical tablets with recoveries ranging from 93.17 to 102.77 and RSD from 1.9 to 2.8%.