Determination of amoxicillin in pharmaceuticals using sequential injection analysis and multivariate curve resolution

In this study, we report a method for quantifying amoxicillin in pharmaceuticals in the presence of interferents using sequential injection analysis (SIA) with a diode-array spectrophotometric detector and multivariate curve resolution with alternating least squares (MCR-ALS). With a suitable analytical sequence, we can use SIA to generate a pH gradient and, for each sample, obtain a data matrix. We used augmented matrices to resolve the system and obtain the spectra and concentration profiles of the components in the sample.We studied what are the effects of imposing trilinearity at the resolution stage, how to choose the species that will be used for quantification (acid, basic or the sum of the two), and which is the most suitable concentration of the reference standard. Once the optimum conditions were established, we performed the quantification in three amoxicillin-containing pharmaceuticals (flubiotic, augmentine, and clamoxyl). With this method, determination is quick, the reactants and instrumentation are inexpensive, and pretreatment of the sample is unnecessary.     

Determination of Allura Red and Tartrazine in Food Samples by Sequential Injection Analysis Combined with Voltammetric Detection at Antimony Film Electrode

An antimony film electrode prepared on‐line and installed as part of a sequential injection system, was used as an electrochemical detector to determine azo dyes in food samples. The influence of several flow variables were evaluated using a central composite design. In optimal conditions, the linear range of the calibration curve varied from 1–5 µM, with a limit of detection limit of 0.3 µM. The relative standard deviation of analytical repeatability was <5.0 %.The method was validated by comparing the results obtained with those provided by HPLC; no significant difference were seen.     

Automated in-syringe single-drop head-space micro-extraction applied to the determination of ethanol in wine samples

A novel approach of head-space single-drop micro-extraction applied to the determination of ethanol in wine is presented. For the first time, the syringe of an automated syringe pump was used as an extraction chamber of adaptable size for a volatile analyte. This approach enabled to apply negative pressure during the enrichment step, which favored the evaporation of the analyte. Placing a slowly spinning magnetic stirring bar inside the syringe, effective syringe cleaning as well as mixing of the sample with buffer solution to suppress the interference of acetic acid was achieved.     

Pressure-assisted capillary electrophoresis for cation separations using a sequential injection analysis manifold and contactless conductivity detection

Pressure assisted capillary electrophoresis in capillaries with internal diameters of 10 μm was found possible without significant penalty in terms of separation efficiency and sensitivity when using contactless conductivity detection. A sequential injection analysis manifold consisting of a syringe pump and valves was used to impose a hydrodynamic flow in the separation of some inorganic as well as organic cations. It is demonstrated that the approach may be used to optimize analysis time by superimposing a hydrodynamic flow parallel to the electrokinetic motion. It is also possible to improve the separation by using the forced flow to maintain the analytes in the capillary, and thus the separation field, for longer times. The use of the syringe pump allows flexible and precise control of the pressure, so that it is possible to impose pressure steps during the separation. The use of this was demonstrated for the speeding up of late peaks, or forcing repeated passage of the sample plug through the capillary in order to increase separation.     

Scientometric Picture of the Evolution of the Literature of Automation in Spectroscopy and Its Current State

The current study focuses on the status of automation and mechanization in spectroscopy for analytical chemistry publications compiled during the period 1980–2006, in Analytical Abstracts. Flow injection analysis (FIA), sequential injection analysis (SIA), multicommutation, and monosegmented and segmented flow strategies were considered. For assessing the evolution of scientific productivity, the total number of publications concerned with the different methodologies was evaluated. In order to provide a picture of the state of the art of this field, the most important journals, the most active authors, and the most productive countries in the field of automation were evaluated in the period of the first years of this century.     

微顺序注射-分光光度法快速测定海水中总磷

基于微顺序注射-阀上实验室,采用磷钼蓝分光光度法测定了海水中总磷,对实验参数进行了优化,并选取了海水中主要成分离子进行了干扰实验。结果表明,海水中总磷质量浓度在0.009~1mg/L范围内与吸光度呈线性关系(r=0.9995),方法的检出限为0.003mg/L。该法测定秦皇岛黄金海岸表层海水中总磷浓度为0.090mg/L,与国标法测定结果0.088mg/L无显著性差异;测定含磷浓度为0.20mg/L的人工海水,相对标准偏差(RSD)为2.4%,样品加标回收率为94.4%~95.7%;海水中主要离子对本实验方法测定产生的干扰在5%以内。     

Autoadaptative sequential injection system for nitrite determination in wastewaters

A novel autoadaptative sequential injection system for the analysis of nitrite is described. The automatic determination uses a direct spectrophotometric method, based on the Griess-Ilosvay reaction. In this method the absorbance of the purple azo dye formed is measured at 555 nm. In the sequential injection operation, the sample and the reagent are aspirated and mixed by reverse flow. The sequencing and overlapping of stacked (reagent) zones as well as selection of volumes have been studied in detail. The proposed analytical system is intelligent, simple and robust, allowing for nitrite determination in a double concentration range, by a simple and automatic programmable operation change. These two ranges are 0.0-3.0 and 0.0-20.0 ppm with detection limits being 0.048 and 0.4 ppm, respectively. Next surroundings have been developed allowing autocalibration and independent monitoring of nitrite concentration. The experimental set-up has been evaluated applying it to real samples analysis of very diverse concentration samples coming from a WWTP. The throughput of the method was 12 samples per hour.     

Sequential injection system for on-line analysis of total nitrogen with UV-mineralization

An automatic method for the determination of total nitrogen in wastewater by sequential injection analysis and mineralization with UV radiation has been developed. The method is based on the mineralization of the samples with sodium persulphate in basic medium under UV radiation. Small volumes of sample and reagents are firstly aspirated into a single channel and then propelled by flow reversal to the UV reactor and then to the detector. The organic and inorganic nitrogen compounds are oxidized to nitrate that is then measured at 226 nm. The sequential injection procedure has been optimized and the factors affecting the efficiency of the oxidation have been studied with a number of test substances with different chemical structures and properties. Solutions in the concentration range 1-56 g l⁻¹ of nitrogen can be analyzed with the described procedure. The sample rate is of 30-40 samples h⁻¹. The LOD is 0.6 mg l⁻¹ N and the reproducibility is 1.8% (28 mg l⁻¹ N). Organic carbon in the form of glucose was added to a number of test solutions to study the potential interference of organic matter.The method was compared with the Kjeldahl digestion method by analyzing 15 wastewater samples with both methods. The nitrate and nitrite content of the non-oxidized samples were subtracted from the corresponding nitrogen content determined after photo-oxidation and the value compared with the Kjeldahl nitrogen content.     

Optimization by means of responses surface of an analytical sequence using a sequential injection system

An experimental design method was applied to determine the optimum working conditions for sequential injection analysis (SIA) to obtain second-order data that will be treated using multivariate curve resolution with alternating least squares (MCR-ALS).

The critical step is to design an analytical sequence that provides relevant information. This sequence depends on parameters related to the system, the chemical reaction, and the chemometric treatment of the data. Also, from the multiple responses that quantify the quality of this analytical sequence, a single response is determined from the desirability function.

This method involves a factor-screening step, in which both the global desirability function and the individual responses are considered and a response surface-modelling step, in which the most relevant factors are considered.     

Sensitive sequential injection determination of naproxen based on interaction with beta-cyclodextrin

A sensitive sequential injection analysis (SIA) methodology for the fluorimetric determination of naproxen is proposed. The developed automatic analytical procedure is based on the complexation of naproxen with β-cyclodextrin (β-CD) yielding an enhanced fluorimetric signal (λ_ex = 280 nm, λ_em = 356 nm).Linear calibration plots were obtained for naproxen concentrations up to 1 × 10⁻⁵ mol l⁻¹. The developed methodology exhibited a good precision, with a R.S.D. < 2.1% (n = 15). The detection limit of the determination was 1.9 × 10⁻⁷ mol l⁻¹ with a sampling rate of about 70 h⁻¹. The automatic method was applied to the determination of naproxen in pharmaceutical formulations. The obtained results were compared with those furnished by the reference procedure and the relative deviations were lower than 3.6%. No interference was found from the excipients usually used in solid pharmaceutical formulations.