Analytica Chimica Acta (v.907, #C)
Editorial board (iii).
Capillary isotachophoresis with ESI-MS detection: Methodology for highly sensitive analysis of ibuprofen and diclofenac in waters by Zdena Malá; Petr Gebauer; Petr Boček (1-6).
The possibilities of reaching higher sensitivity in capillary electrophoretic analyses of complex samples with ESI-MS detection were investigated on the example of analysis of diclofenac and ibuprofen in waters. The applied separation approach is based on application of isotachophoresis that ensures permanent stacking of analytes until they reach the detector. Investigation of the possibilities of MS detector optimization have shown that optimization of fragmentor voltage and working in the SIM mode with collection of data for multiple fragments both increases the method specificity and approx. doubles its sensitivity. Combination with an offline SPE preconcentration step resulted in very high sensitivity of the described methodology with a reached LOD below 2 × 10−12 M, corresponding to analyte levels of 0.6 ng L−1 of diclofenac and 0.4 ng L−1 of ibuprofen. The results demonstrate that CE-MS, particularly when performed in the ITP mode, has the potential to reach sensitivities comparable to HPLC-MS.Display Omitted
Keywords: Isotachophoresis; Mass spectrometric detection; Solid phase extraction; Water analysis; Diclofenac; Ibuprofen;
A review of chemical gradient systems for cell analysis by Himali Somaweera; Akif Ibraguimov; Dimitri Pappas (7-17).
Microfluidic spatial and temporal gradient generators have played an important role in many biological assays such as in the analysis of wound healing, inflammation, and cancer metastasis. Chemical gradient systems can also be applied to other fields such as drug design, chemical synthesis, chemotaxis, etc. Microfluidic systems are particularly amenable to gradient formation, as the length scales used in chips enable fluid processes that cannot be conducted in bulk scale. In this review we discuss new microfluidic devices for gradient generation and applications of those systems in cell analysis.Display Omitted
Keywords: Gradient; Microfluidics; Lab on a chip; Review;
Automation of static and dynamic non-dispersive liquid phase microextraction. Part 2: Approaches based on impregnated membranes and porous supports by Michal Alexovič; Burkhard Horstkotte; Petr Solich; Ján Sabo (18-30).
A critical overview on automation of modern liquid phase microextraction (LPME) approaches based on the liquid impregnation of porous sorbents and membranes is presented. It is the continuation of part 1, in which non-dispersive LPME techniques based on the use of the extraction phase (EP) in the form of drop, plug, film, or microflow have been surveyed.Compared to the approaches described in part 1, porous materials provide an improved support for the EP. Simultaneously they allow to enlarge its contact surface and to reduce the risk of loss by incident flow or by components of surrounding matrix. Solvent-impregnated membranes or hollow fibres are further ideally suited for analyte extraction with simultaneous or subsequent back-extraction. Their use can therefore improve the procedure robustness and reproducibility as well as it “opens the door” to the new operation modes and fields of application. However, additional work and time are required for membrane replacement and renewed impregnation.Automation of porous support-based and membrane-based approaches plays an important role in the achievement of better reliability, rapidness, and reproducibility compared to manual assays. Automated renewal of the extraction solvent and coupling of sample pretreatment with the detection instrumentation can be named as examples.The different LPME methodologies using impregnated membranes and porous supports for the extraction phase and the different strategies of their automation, and their analytical applications are comprehensively described and discussed in this part. Finally, an outlook on future demands and perspectives of LPME techniques from both parts as a promising area in the field of sample pretreatment is given.Display Omitted
Keywords: Automation; Miniaturisation; Liquid phase microextraction; Supported liquid membrane microextraction; Chromatomembrane; Hollow-fibre liquid phase microextraction; Static liquid phase microextraction; Dynamic liquid phase microextraction;
Sampling frequency, response times and embedded signal filtration in fast, high efficiency liquid chromatography: A tutorial by M. Farooq Wahab; Purnendu K. Dasgupta; Akinde F. Kadjo; Daniel W. Armstrong (31-44).
With increasingly efficient columns, eluite peaks are increasingly narrower. To take full advantage of this, choice of the detector response time and the data acquisition rate a.k.a. detector sampling frequency, have become increasingly important. In this work, we revisit the concept of data sampling from the theorem variously attributed to Whittaker, Nyquist, Kotelnikov, and Shannon. Focusing on time scales relevant to the current practice of high performance liquid chromatography (HPLC) and optical absorbance detection (the most commonly used method), even for very narrow simulated peaks Fourier transformation shows that theoretical minimum sampling frequency is still relatively low (<10 Hz). However, this consideration alone may not be adequate for real chromatograms when an appreciable amount of noise is present. Further, depending on the instrument, the manufacturer's choice of a particular data bunching/integration/response time condition may be integrally coupled to the sampling frequency. In any case, the exact nature of signal filtration often occurs in a manner neither transparent to nor controllable by the user. Using fast chromatography on a state-of-the-art column (38,000 plates), we evaluate the responses produced by different present generation instruments, each with their unique black box digital filters. We show that the common wisdom of sampling 20 points per peak can be inadequate for high efficiency columns and that the sampling frequency and response choices do affect the peak shape. If the sampling frequency is too low or response time is too large, the observed peak shapes will not remain as narrow as they really are – this is especially true for high efficiency and high speed separations. It is shown that both sampling frequency and digital filtering affect the retention time, noise amplitude, peak shape and width in a complex fashion. We show how a square-wave driven light emitting diode source can reveal the nature of the embedded filter. We discuss time uncertainties related to the choice of sampling frequency. Finally, we suggest steps to obtain optimum results from a given system.Display Omitted
Keywords: High-efficiency chromatography; Fast separations; Sampling theorem; Response times; Digital filters;
Total phenol analysis of weakly supported water using a laccase-based microband biosensor by Alina N. Sekretaryova; Anton V. Volkov; Igor V. Zozoulenko; Anthony P.F. Turner; Mikhail Yu Vagin; Mats Eriksson (45-53).
The monitoring of phenolic compounds in wastewaters in a simple manner is of great importance for environmental control. Here, a novel screen printed laccase-based microband array for in situ, total phenol estimation in wastewaters and for water quality monitoring without additional sample pre-treatment is presented. Numerical simulations using the finite element method were utilized for the characterization of micro-scale graphite electrodes. Anodization followed by covalent modification was used for the electrode functionalization with laccase. The functionalization efficiency and the electrochemical performance in direct and catechol-mediated oxygen reduction were studied at the microband laccase electrodes and compared with macro-scale electrode structures. The reduction of the dimensions of the enzyme biosensor, when used under optimized conditions, led to a significant improvement in its analytical characteristics. The elaborated microsensor showed fast responses towards catechol additions to tap water – a weakly supported medium – characterized by a linear range from 0.2 to 10 μM, a sensitivity of 1.35 ± 0.4 A M−1 cm−2 and a dynamic range up to 43 μM. This enhanced laccase-based microsensor was used for water quality monitoring and its performance for total phenol analysis of wastewater samples from different stages of the cleaning process was compared to a standard method.Display Omitted
Keywords: Laccase; Microelectrode; Microband; Electrochemical modeling; Total phenol analysis; Wastewater;
A fully automated effervescence-assisted switchable solvent-based liquid phase microextraction procedure: Liquid chromatographic determination of ofloxacin in human urine samples by Christina Vakh; Aleksei Pochivalov; Vasil Andruch; Leonid Moskvin; Andrey Bulatov (54-59).
A novel fully automated effervescence-assisted switchable solvent-based liquid phase microextraction procedure has been suggested. In this extraction method, medium-chain saturated fatty acids were investigated as switchable hydrophilicity solvents. The conversion of fatty acid into hydrophilic form was carried out in the presence of sodium carbonate. The injection of sulfuric acid into the solution decreased the pH value of the solution, thus, microdroplets of the fatty acid were generated. Carbon dioxide bubbles were generated in-situ, and promoted the extraction process and final phase separation. The performance of the suggested approach was demonstrated by the determination of ofloxacin in human urine samples using high-performance liquid chromatography with fluorescence detection. This analytical task was used as a proof-of-concept example. Under the optimal conditions, the detector response of ofloxacin was linear in the concentration ranges of 3·10−8−3·10−6 mol L−1. The limit of detection, calculated from a blank test based on 3σ, was 1·10−8 mol L−1. The results demonstrated that the presented approach is highly cost-effective, simple, rapid and environmentally friendly.Display Omitted
Keywords: Effervescence-assisted switchable solvent-based liquid phase microextraction; Green analytical chemistry; Flow analysis; Fatty acids; Ofloxacin; Urine;
Stepped MSAll Relied Transition (SMART): An approach to rapidly determine optimal multiple reaction monitoring mass spectrometry parameters for small molecules by Hui Ye; Lin Zhu; Lin Wang; Huiying Liu; Jun Zhang; Mengqiu Wu; Guangji Wang; Haiping Hao (60-68).
Multiple reaction monitoring (MRM) is a universal approach for quantitative analysis because of its high specificity and sensitivity. Nevertheless, optimization of MRM parameters remains as a time and labor-intensive task particularly in multiplexed quantitative analysis of small molecules in complex mixtures. In this study, we have developed an approach named Stepped MSAll Relied Transition (SMART) to predict the optimal MRM parameters of small molecules. SMART requires firstly a rapid and high-throughput analysis of samples using a Stepped MSAll technique (sMSAll) on a Q-TOF, which consists of serial MSAll events acquired from low CE to gradually stepped-up CE values in a cycle. The optimal CE values can then be determined by comparing the extracted ion chromatograms for the ion pairs of interest among serial scans. The SMART-predicted parameters were found to agree well with the parameters optimized on a triple quadrupole from the same vendor using a mixture of standards. The parameters optimized on a triple quadrupole from a different vendor was also employed for comparison, and found to be linearly correlated with the SMART-predicted parameters, suggesting the potential applications of the SMART approach among different instrumental platforms. This approach was further validated by applying to simultaneous quantification of 31 herbal components in the plasma of rats treated with a herbal prescription. Because the sMSAll acquisition can be accomplished in a single run for multiple components independent of standards, the SMART approach are expected to find its wide application in the multiplexed quantitative analysis of complex mixtures.Display Omitted
Keywords: Stepped MSAll; Stepped MSAll Relied Transition (SMART); Multiple reaction monitoring (MRM); Q-TOF; Quantitative analysis; Complex mixture;
Facile synthesis of hydrophilic polyamidoxime polymers as a novel solid-phase extraction matrix for sequential characterization of glyco- and phosphoproteomes by Jiaxi Wang; Yanan Wang; Mingxia Gao; Xiangmin Zhang; Pengyuan Yang (69-76).
Selective enrichment of glycopeptides or phosphopeptides with great biological significance is essential for high-throughput mass spectrometry analysis. However, most previously reported methods only focused on enriching either glycopeptides or phosphopeptides rather than enriching them both. In this work, for the first time, a facile route was developed for the synthesis of polyamidoxime polymers with intrinsic hydrophilic skeletons and attractive long chain structure. The polyamidoxime materials (co-PAN) were synthesized from polyacrylonitrile (PAN) precursor and were successfully used for selective enrichment of glycopeptides. After that, co-PAN as a matrix functionalized with titanium ions (co-PAN@Ti4+) could efficiently enrich phosphopeptides. The performances of the polymers for sequential selective and effective enrichment of glycopeptides and phosphopeptides were evaluated with standard peptide mixtures and human serum. Moreover, the efficiency of enrichment of the material was still retained after being used repeatedly. These results demonstrated that the polymers showed great potential in the practical application of proteomics.Display Omitted
Keywords: Hydrophilic polyamidoxime polymers; Sequential characterization; Glycopeptides; Phosphopeptides; Mass spectrometry;