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In recent years, the development of peptide drugs and alternative routes of administration, such as buccal and sublingual routes, has become increasingly important to the pharmaceutical industry. Performing experiments under physiologically relevant conditions is still a challenge that has not yet been fully mastered. The requirements associated with these alternative administration routes (e.g. permeation testing for buccal administration) push common analytical detection systems in pharmaceutical technology to their limits, especially with regard to large molecules and peptides. An HPLC-coupled coaxial liquid-core waveguide fluorescence detector has been developed and evaluated within this study to overcome these limits by achieving a more sensitive detection. Desmopressin acetate was selected as the peptide drug with the aim of investigating its permeation behavior during the clinically relevant application period of one hour. Based on the detector system, a complete validation according to the requirements of international guidelines was successfully performed. learn more The results of the validation showed an increase in sensitivity resulting in a limit of detection of 4.7 ng/mL and a lower limit of quantification of 9.5 ng/mL. Moreover, it has been demonstrated that the permeation of desmopressin can be observed in clinically relevant dosages and time periods of up to one hour using this innovative detector system.Paprika is considered a high-quality product being one of the most consumed spices in the world. Contamination with mycotoxins may appear due to inappropriate practices during processing or resulting from invading mould in the final manufactured products. A sample treatment based on dispersive magnetic solid-phase extraction (DMSPE) has been proposed for emerging mycotoxin determination, enniatins (ENNs) and beauvericins (BEAs), in paprika. Different magnetic nanoparticles were tested, and cellulose-ferrite nanocomposite was selected for the extraction and preconcentration of the mycotoxins. Nanocomposite was characterised using field emission scanning electron microscopy and energy dispersive X-ray spectroscopy in terms of morphology and elemental composition. High-resolution mass spectrometry allowed the quantification of the five main emerging mycotoxins and the monitoring of unexpected members of this class of toxic fungal secondary metabolites. The method has been validated, obtaining limits of quantification between 9.5 and 9.9 μg kg-1 and testing its trueness through recovery studies, with satisfactory values of between 89.5 and 97.7%. Relative standard deviations were calculated to evaluate the intra- and inter-day precision and values lower than 8% were obtained in all cases. The analysis of 26 samples, including conventional and organic, demonstrated the presence of ENNB1 at 12.0 ± 0.6 μg kg-1 in one of the samples studied. Other analogues ENNs and BEAs were not detected.Many phosphoprotein biomarkers have been proved to exist in body fluids such as serum and urine, however, there is absence of rapid and efficient separation and identification method. In this study, we proposed to combine metal oxide affinity chromatography (MOAC), molecular imprinting technology (MIT) and matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS) to establish an effective approach to solve this problem. To verify the feasibility of this approach, we selected a typical phosphoprotein lysozyme (Lys) as template and magnetic TiO2 as substrate to prepare the molecularly imprinted nanoparticles (denoted as Fe3O4@TiO2@Lys MIPs). A point worth noting is that polydopamine (PDA) as polymer layer made Fe3O4@TiO2@Lys MIPs more hydrophilic and biocompatible. Thanks to the recognition sites of phosphate and the template-shaped cavities, Fe3O4@TiO2@Lys MIPs showed great sensitivity (0.01 ng*μL-1) and selectivity (Lysozyme BSA β-casein = 1100100, mass ratio) in standard phosphoprotein solution. At the end, the Fe3O4@TiO2@Lys MIPs showed great separation ability to lysozyme phosphoprotein in both human serum and urine samples. Therefore, the MOAC-based molecularly imprinted approach is worthy to be expected in effective separation of phosphoprotein biomarker in complex body fluid, which will be a promising one in future.The preparation of well-defined new hydrophilic molecularly imprinted polymer (MIP) microspheres and their use as the dispersive solid-phase microextraction (dSPME) sorbents for direct and selective drug (i.e., propranolol) capture from the undiluted bovine serum are described. These MIPs have surface-grafted dense poly(2-hydroxyethyl methacrylate) (PHEMA) brushes with different molecular weights and grafting densities. They were readily prepared via the facile reversible addition-fragmentation chain transfer (RAFT) coupling chemistry. Both the molecular weights and grafting densities of PHEMA brushes showed significant influence on their complex biological sample-compatibility, and only those MIPs bearing PHEMA brushes with high enough molecular weights and grafting densities could selectively recognize propranolol in the undiluted pure milk and bovine serum. In particular, they have proven to be highly versatile dSPME sorbents for directly and selectively capturing propranolol from the undiluted bovine serum with satisfactory recoveries (85.2-97.4%) and high accuracy (RSD = 2.3-3.7%), even in the presence of one analogue of propranolol. The limit of detection was 0.002 μM with a linear correlation coefficient of 0.9994 in the range of 0.01-100 μM. Excellent precision was verified by both the intraday and interday analytical results. Their good reusability was also confirmed. This work demonstrates the high potential of such hydrophilic MIP-based dSPME sorbents for rapid, accurate, and reliable drug determination in complex biological samples.Electrochemical conversion of fesoterodine to one of its oxidation products was evaluated with the application of the wall-jet flow cell. A traditional, "static" mode of electrolysis was compared with the "dynamic" mode of cell performance. For statistical assessment of the data, experiments were planned and performed with the application of design of experiments approach, namely Taguchi L18 design. After screening phase, the experimental settings were broadened or adjusted according to the results and optimization was performed. All of the samples were electrolysed with the use of chronoamperometric method in a three electrode system. The electrolysed samples were analysed using UHPLC-PDA-QDA method. The chromatographic run was performed in gradient elution with the application of C8 column. The response was expressed as % area of the main peak found with the PDA detection method whereas QDA detector was used in positive SIM mode for structural confirmation. All data obtained for both screening and optimization were treated together and linear models were adjusted.
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