Liquid chromatography coupled to on-line post column derivatization for the determination of organic compounds: A review on instrumentation and chemistries

Analytical derivatization either in pre or post column modes is one of the most widely used sample pretreatment techniques coupled to liquid chromatography. In the present review article we selected to discuss the post column derivatization mode for the analysis of organic compounds. The first part of the review focuses to the instrumentation of post-column setups including not only fundamental components such as pumps and reactors but also less common parts such as static mixers and back-pressure regulators; the second part of the article discusses the most popular “chemistries” that are involved in post column applications, including reagent-less approaches and new sensing platforms such as the popular gold nanoparticles. Some representative recent applications are also presented as tables.     

Synthesis and characterization of poly(N-methylpyrrole)/TiO2 composites on steel

Poly(N-methyl pyrrole) coating was successfully electrodeposited on steel substrates in mixed electrolytes of dodecyl benzene sulphonic acid (DBSA) with oxalic acid in the absence and the presence of TiO₂ nanoparticles (NPs). The morphology and compositions were characterized by Field Emission Scanning Electron Microscopy (FESEM), Fourier Transform Infrared Spectroscopy (FTIR), Energy-Dispersive X-ray spectroscopy (EDX). X-ray Diffraction (XRD) and Transmission Electron Microscopy (TEM) were used to calculate the size of nanoparticles. Electrode/polymer/electrolyte system was studied by Electrochemical Impedance Spectroscopy (EIS). The FESEM micrographs suggest that the incorporation of TiO₂ nanoparticles affects the morphology of the film significantly and makes the TiO₂ to be loosely piled up with PMPy. The results of EIS showed that synthesized PMPy in the presence of TiO₂ NPs increases and decreases the R_po and C_c of the coating respectively. The increase of the area of synthesized PMPy in the presence of nanoparticles can increase its ability to interact with the ions liberated during the corrosion reaction of steel in NaCl solution.     

芦丁在铂纳米/碳纳米管修饰电极上电化学行为研究

通过电沉积的方式在多壁碳纳米管(MWCNTs)修饰玻碳电极表面上沉积铂(pt)纳米粒子,并运用循环伏安法(CV)、示差脉冲伏安法(DPV)探讨了芦丁在铂纳米/碳纳米管/玻碳电极上的电化学行为.实验结果表明,芦丁在该修饰电极上呈现一对良好氧化还原峰,其氧化峰电流与浓度在3.2×10(-8)～1.2×10(-5)mol/L...     

Cadmium Tellurium Quantum Dots in Sol-Gel-Derived Silica Spheres Coated with Calix[6]Arene as an Optical Probe for Dalapon

This paper reports a new optical probe for detect dalapon. We have synthesized the luminescent and stable CdTe quantum dots(QDs) capped with calix[6]arene(C[6]/SiO₂/CdTe) via the sol-gel technique in aqueous media. These hybrid organic-inorganic compounds are characterized by IR spectroscopy, ultraviolet-visible spectroscopy (UV-vis), transmission electron microscopy (TEM), and fluorescence. We found that the C[6]/SiO₂/CdTe were more stable and had higher fluorescence than the SiO₂/CdTe nanoparticles (NPs). The C[6]/SiO₂/CdTe show selectivity and sensitivity to dalapon via significant fluorescence intensity decrease. It can be ascribed to the Stern-Volmer equation. Under the optimal conditions, the relative fluorescent intensity was decreased linearly with increasing dalapon concentration in the range of 1.0–25.0 nmol/L with a detection limit of 0.262 nmol/L of dalapon. The possible underlying mechanism is discussed by Langmuir binding isotherm.     

Green Synthesis of Silver Nanoparticles at Room Temperature Using Kiwifruit Juice

Comparing with physical and chemical methods, green synthesis techniques are emerging as facile and eco-friendly methods for the synthesis of silver nanoparticles. In this work, we demonstrated the biological synthesis of silver nanoparticles by the reduction of silver ions using kiwifruit juice as the reducing and stabilizing reagent. From the evidence of ultraviolet-visible spectroscopy and transmission electron microscopy, different sizes of silver nanoparticles were formed when the juice volume, reaction temperature, and reaction time were altered with respect to 0.01% silver acetate solution. The synthesized silver nanoparticles were stable for more than 1 month. Transmission electron microscopy studies showed the silver nanoparticles synthesized in room temperature have the diameters in the range of 5–25 nm. The proposed synthesis method is green and low cost, and the synthesized silver nanoparticles have potential bioanalytical applications.     

Au@SiO2 core/shell nanoparticle assemblage used for highly sensitive SERS‐based determination of glucose and uric acid

The use of Au@SiO₂ core/shell nanoparticle (NP) assemblage with highly sensitive surface‐enhanced Raman scattering (SERS) was investigated for the determination of glucose and uric acid in this study. Rhodamine 6G dye molecules were used to evaluate the SERS enhancement factor for the synthesized Au@SiO₂ core/shell NPs with various silica shell thicknesses. The enhancement of SERS signal from Rhodamine 6G was found to increase with a decrease in the shell thickness. The core/shell assemblage with silica layer of 1–2 nm over a Au NP of ~36 nm showed the highest SERS signal. Our results show that the SERS technique is able to detect glucose and uric acid within wide concentration ranges, i.e. 20 ng/dL to 20 mg/dL (10⁻¹²–10⁻³ M) and 16.8 ng/dL to 2.9 mg/dL (10⁻¹¹–1.72 × 10⁻⁴ M), respectively, with associated lower detection limits of ~20 ng/dL (~1.0 × 10⁻¹² M) and ~16.8 ng/dL (~1.0 × 10⁻¹¹ M). Our work offers a low‐cost route to the fabrication of agile sensing devices applicable to the monitoring of disease progression. Copyright © 2013 John Wiley & Sons, Ltd.     

Amperometric Biosensor Based on Immobilization Acetylcholinesterase on Manganese Porphyrin Nanoparticles for Detection of Trichlorfon with Flow‐Injection Analysis System

A highly sensitive amperometric biosensor for the detection of organophosphate pesticides (OPs) is developed. The biosensor was fabricated by immobilized acetylcholinesterase (AChE) on manganese (III) meso‐tetraphenylporphyrin (MnTPP) nanoparticles (NPs)‐modified glassy carbon (GC) electrode. The MnTPP NPs used in this article were synthesized by mixing solvent techniques. AChE enzyme was immobilized on the MnTPP NPs surface by conjugated with chitosan (CHIT). The electrocatalytic activity of MnTPP NPs led to a greatly improved performance for thiocholine (TCh) product detection. The developed AChE‐CHIT/MnTPPNP/GC biosensor integrated with a flow‐injection analysis (FIA) system was used to monitor trichlorfon (typical OP). A wide linear inhibition response for trichlorfon is observed in the range of 1.0 nM–1.0 mM, corresponding to 10–83% inhibition for AChE with a detection limit of 0.5 nM.     

Detection of ferulic acid based on the plasmon resonance light scattering of silver nanoparticles

In this contribution, a plasmon resonance light scattering (PRLS) detection method of ferulic acid (FA) is proposed based on the formation of silver nanoparticles (NPs). It was found that, FA acted as a reducing agent in alkaline medium and could be oxidized by AgNO₃, resulting in the formation of silver NPs. The formed silver NPs, which were identified by measuring the plasmon resonance absorption spectra, PRLS spectra and transmission electron microscopy (TEM) image, display characteristic plasmon resonance optical absorption and PRLS band in the visible region. It was found that the PRLS intensity, which could be easily measured using a common spectrofluorometer, was in proportion to the concentration of FA over the range from 0.2 to 2.0 μmol l⁻¹ with the corresponding limits of determination (3σ) of 15.2 nmol l⁻¹. With that, ferulate sodium injection samples have been detected with R.S.D. lower than 3.0% and recoveries over the range of 101.2–104.5%. On the other hand, the present reaction maybe provides the basis of an environmentally friendly approach for the synthesization of silver NPs.     

Electrochemical determination of nitrate on Ag nanoparticles-decorated poly (direct blue 15) electrodes

In this study, for the first time, the electro-polymerization of Direct blue15 (DB15), an azo dye, was carried out on the surface of ITO. Furthermore, the poly(DB15) surface was electrochemically decorated with Ag nanoparticles (AgNPs), and the fabricated AgNPs/PDB15 electrodes were examined as nitrate sensors. Compared to unmodified ITO electrode, the AgNPs/PDB15 electrode had greatly improved electrochemical response to nitrate reduction. The nitrate determination in a linear range from 1.0×10⁻⁵ mol L⁻¹ to 2.27×10⁻³ mol L⁻¹ was performed with a detection limit of 9.66 μM. The synthesized electrode is a promising sensor for the electrochemical detection of nitrate pollutants in water.     

Efficient photodegradation of methyl orange and bactericidal activity of Ag doped ZnO nanoparticles

In the present work, silver-doped ZnO (Ag–ZnO NPs) with different concentrations of silver ions (0.3, 0.5, 1.0 and 1.5 mol %) were synthesized by using a simple co-precipitation method. The Ag–ZnO NPs were primarily characterized by XRD, FT-IR, SEM, EDS, TEM, UV–Vis. DRS, PL and BET surface area. The XRD analysis of Ag–ZnO NPs shows a wurtzite structure and optimized Ag–ZnO NPs (1.0 mol %) exhibit a lower crystallite size of 15.96 nm than that of bare ZnO (19.07 nm). Optical study shows a decrease in band gap from 3.13 to 2.97 eV as the concentration of Ag ions increases from 0.3 to 1.5 mol%. TEM images reveal the spherical shape particle with sizes ranging between 10 and 15 nm. From the multipoint BET plot, the surface area of Ag–ZnO NPs found 38.06 m²/gwhich is higher than the ZnO NPs (34.48 m²/g). The photocatalytic study demonstrated that the Ag–ZnO NPs (1.0 mol %) has an excellent photodegradation efficiency of Methyl Orange (96.74%)with a 26% increment as compared to bare ZnO (70.47%). Furthermore, the bactericidal activity of Ag–ZnO NPs (1.0 mol %) was investigated against four different bacterial strains. The results explored that the Gram-negative bacteria (E. coli and P. vulgaris) are more sensitive than Gram-positive (S. aureus and B. cereus) to Ag–ZnO NPs. Overall, the anticipated material is economical and reusable for photodegradation and antibacterial activity.