Analytical Chemistry Research最新文献

It is well known that surfactant-suspended carbon nanotube (CNT) samples can be purified by centrifugation to decrease agglomerates and increase individually-dispersed CNTs. However, centrifugation is not always part of protocols to prepare CNT samples used in biomedical applications. Herein, using carboxylated multi-walled CNTs (cMWCNTs) suspended in water without a surfactant, we developed a Boehm titrimetric method for the analysis of centrifuged cMWCNT suspensions and used it to show that the surface acidity of oxidized carbon materials in aqueous cMWCNT suspensions was enriched by ∼40% by a single low-speed centrifugation step. This significant difference in surface acidity between un-centrifuged and centrifuged cMWCNT suspensions has not been previously appreciated and is important because the degree of surface acidity is known to affect the interactions of cMWCNTs with biological systems.

We investigated the process of a bromination reaction of malonic acid and methylmalonic acid in the Belousov-Zhabotinsky reaction by using a quartz crystal microbalance (QCM). The process involves an enolization reaction as a rate-determining step. We found that, in the step, the variation of Br₂ concentration induced an exactly quantitative shift of a resonant frequency of the QCM, based on the change of the surface mass on the QCM and the solution viscosity and density. This new finding enabled us to estimate the reaction rate constants and the thermodynamic parameters of the enolization reaction due to a QCM measurement. The values measured by the QCM were in good agreement with those measured by a UV-spectrophotometer. As a result, we succeeded to develop a new measurement method of a nonlinear chemical reaction.

This paper describes basic characteristics of the quartz crystal sensor with interdigitated electrodes (IDE quartz crystal sensor) which is for simultaneous monitoring of mass, viscosity, conductivity and dielectric changes of liquids or thin films. As the IDE quartz crystal sensor has three terminals for a pair of IDEs on the one side and a counter electrode on the other side, the resonance properties have been analyzed using the electrical equivalent circuit models and measured experimentally for all connecting types of electrode pairs. The IDE quartz crystal has shown clear resonance curves for calculating the resonance frequency and resonance resistance values as well as normal quartz crystal in the air and in contact with liquid. Small shifts in the resonance frequency and resonance resistance depending on the connecting types have been obtained and analyzed using the equivalent circuit models. We have found the integrated quartz crystal and IDE sensors could be monitored simultaneously by only one impedance analyzer. Finally, two types of measuring systems have been demonstrated for continuous measuring methods.

The electrochemical behavior of kaempferol was investigated by cyclic voltammetry (CV) and square wave voltammetry (SWV) at plane and multiwalled carbon nanotubes modified carbon paste electrode (MWCNTs/CPE). Kaempferol produces an anodic peak at MWCNTs modified CPE with a quasi-reversible nature in phosphate buffer of pH 7.73. The oxidized species of kaempferol was found to be stable (Ip^a/Ip^c ≈1) over scan rates of 100∼600 mV⁻¹. The same electrode was also found to catalyze the electrode oxidation of quercetin in presence of kaempferol under similar conditions which enabled the simultaneous determination of kaempferol and quercetin. Linearity of peak currents (Ip) vs. concentrations of kaempferol and quercetin was found in the range of 6.72 × 10⁻⁹ M to 40.34 × 10⁻⁹ M with a detection limit of 2.90 × 10⁻⁹ M for kaempferol and 13.0 × 10⁻⁹ M to 50.9 × 10⁻⁹ M with a detection limit of 3.5 × 10⁻⁹ M for quercetin using fast and sensitive SWV. The developed method has been applied for the quantitative analysis of kaempferol in corms and petals of Indian traditional medicine saffron (Crocus sativus) using a phosphate buffer of pH 7.73 and the average percent recoveries obtained are 99.84 and 99.26, respectively.

In this study, the organic polymer monolith was developed as a weak anion exchanger column in high performance liquid chromatography for DNA separation. Methacrylate-based monolithic column was prepared in microbore silicosteel column (100 × 0.5 mm i.d.) by in-situ polymerization reaction using glycidyl methacrylate as monomer; ethylene dimethacrylate as crosslinker; 1-propanol, 1,4-butanediol, and water as porogenic solvents, with the presence of initiator α,α′-azobisisobutyronitrile (AIBN). The monolith matrix was modified with diethylamine to create weak anion exchanger via ring opening reaction of epoxy groups. The morphology of the monolithic column was studied by SEM. The properties of the monolithic column, such as permeability, mechanical stability, binding capacity and pore size distribution, were characterized in detail. From the results of the characterization, monoliths poly-(GMA-co-EDMA) with total monomer percentage (%T) 40 and crosslinker percentage (%C) 25 was found to be the ideal composition of monomer and crosslinker. It has good mechanical stability and high permeability, adequate molecular recognition sites (represented with binding capacity value of 36 mg ml⁻¹), and has relatively equal proportion of flow-through pore and mesopores (37.2% and 41.1% respectively). Poly-(GMA-co-EDMA) with %T 40 and %C 25 can successfully separate oligo(dT)_12–18 and 50 bp DNA ladder with good resolution.

Infrared sample digestion technology has been rapidly developed in recent years and its application and digestion performance on a variety of ores of base metals was assessed in this study, using a 6-channel infrared digester. Digestion times of 10 min or less were achieved for all base metal ores investigated, including oxides, sulfides, and silicates of Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Sb, Ti, W, and Zn. Performance criteria for all samples were excellent, reflected in z values of less than 2 in all cases. Various acid digestion methods were developed for the selected ore samples under high intensity infrared radiation and delivered virtually complete recoveries of all of the elements of interest. Chromite, the notoriously refractory chromium ore was digested within 10 min and gave 100% recovery of chromium. These digestions were accomplished without resorting to perchloric acid and, for most sample types, without hydrofluoric acid, significantly improving the workplace safety for analysts. Between-channel variation of the analyte recoveries from the 6-channel unit were generally below 2%, suggesting that the digestion methods developed with this platform provide reproducible results to meet various sample preparation demands. The high speed and analyte recovery of these digestions makes this methodology especially attractive for prospectors and developers who demand rapid and reliable results from exploration samples.

An analytical methodology based on cloud point extraction (CPE) coupled to Ultra-Fast Liquid Chromatography and electrospray tandem mass spectrometry (UFLC-MS/MS) was developed for analysis of Abacavir (ABC), Efavirenz (EFV), Lamivudine (3 TC) and Nelfinavir (NFV) in human plasma. It is the first time that CPE was used for extraction of antiretrovirals (ARV) from plasma. The effects of relevant physic-chemical variables on analytical response of each ARV, including pH, surfactant concentration, equilibration time and temperature, were study and optimized; as well as its coupling to UFLC-ESI-MS/MS. Under optimized conditions, the resulting methodology was as follows: a 500 μL aliquot of human plasma was diluted with 2 mL deionized water in a 10 mL centrifuge tube. A 500 μL aliquot Triton X-114 5% w/v was added and homogenized using a vortex stirrer. The resulting cloudy solution was kept at 65 °C for 20 min for promoting the condensation of surfactant micelles. Then it was centrifuged at 3000 × g for 5 min for separation of the surfactant-rich phase. After discarding the aqueous supernatant, 400 μL ACN were added to the remaining surfactant rich phase and centrifuged in order to precipitate proteins and separate them. A 150 μL aliquot of the supernatant was transferred to 2 mL vial and further diluted with 400 μL deionized water. A 30 μL aliquot of the so-prepared solution was injected and analyzed into the UFLC-MS/MS. The method detection limits for ABC, EFV, 3 TC and NFV under optimized conditions were 31, 77, 57 and 21 ng mL⁻¹, respectively. The RSD% for the studied analytes were <15%, except at the LOQ, which were <19%. Recovery values ranged from 81 to 107%. The proposed methodology was successfully applied for the analysis of ABC, EFV, 3 TC and NFV in human plasma within the concentration range of 43–6816, 125–4992, 81–3248 and 49–7904 ng mL⁻¹, respectively. Under optimized working conditions the proposed analytical methodology meets standard requirements of international guidelines, which makes it suitable for pharmacokinetic studies of the four ARV, as well as for therapeutic monitoring of HIV patients.

In the present work, we have synthesized a new water soluble colorless chemical compound 7-O-tert-butyldiphenylsilyl-4-methylcoumarin (TBDPSC) that releases fluorescent molecules imparting blue fluorescence to the solution, upon interaction with fluoride ions in water. The blue fluorescence can be visualized using simple hand held ultraviolet (UV) lamps. TBDPSC has excellent sensitivity and selectivity towards fluoride and our results indicate that fluoride concentrations as low as 0.2 mg/L can be accurately detected within a few seconds. Fluoride testing with TBDPSC is simple and rapid compared to the conventional methodologies without the requirement of trained personnel. Hence, the present fluoride detection method can be easily field deployable and particularly useful for monitoring water quality in limited resource communities.