Villadsenhoumann7157

Development of effective direct electron transfer is considered an interesting platform to obtain high performance bioelectrodes. Therefore, designing of scalable and cost-effective immobilization routes that promotes correct direct electrical contacting between the electrode material and the redox enzyme is still required. As we present here, electrochemical entrapment of pyrroloquinoline quinone-dependent glucose dehydrogenase (PQQ-GDH) on single-wall carbon nanotube (SWCNT)-modified electrodes was carried out in a single step during electrooxidation of para-aminophenyl phosphonic acid (4-APPA) to obtain active bioelectrodes. The adequate interaction between SWCNTs and the enzyme can be achieved by making use of phosphorus groups introduced during the electrochemical co-deposition of films, improving the electrocatalytic activity towards glucose oxidation. Two different procedures were investigated for electrode fabrication, namely the entrapment of reconstituted holoenzyme (PQQ-GDH) and the entrapment of apoenzyme (apo-GDH) followed by subsequent in situ reconstitution with the redox cofactor PQQ. In both cases, PQQ-GDH preserves its electrocatalytic activity towards glucose oxidation. Moreover, in comparison with a conventional drop-casting method, an important enhancement in sensitivity was obtained for glucose oxidation (981.7 ± 3.5 nA mM-1) using substantially lower amounts of enzyme and cofactor (PQQ). The single step electrochemical entrapment in presence of 4-APPA provides a simple method for the fabrication of enzymatic bioelectrodes.In this paper, Fe3O4@ppy-Pt core-shell nanoparticles (NPs) could be produced and utilized for the development of a novel electrochemical sensor to detect 6-mercaptopurine (6-MP). 6-MP determination was examined by cyclic voltammetry (CV), chronoamperometry (CHA), linear sweep voltammetry (LSV), and differential pulse voltammetry (DPV) at Fe3O4@ppy-Pt core-shell NPs modified screen printed electrode (Fe3O4@ppy-Pt/SPE) in phosphate buffered solution (PBS). The outcomes obtained from DPV demonstrated that the Fe3O4@ppy-Pt/SPE proved a linear concentration range among 0.04 and 330.0 μM having a detection limit of 10.0 nM for 6-MP. Also, modified electrode was satisfactorily utilized to detect 6-MP in the presence of 6-thioguanine (6-TG). This sensor showed two separate oxidative peaks at 530 mV for 6-MP and at 730 mV for 6-TG with a peak potential separation of 200 mV which was large enough for simultaneous detection of the two anticancer drugs. In addition, the proposed sensor presented long-term stability, good repeatability, and excellent reproducibility. Finally, the modified electrode demonstrated satisfactory outcomes while used in real samples, proposing the appropriate potential of Fe3O4@ppy-Pt/SPE in the case of clinical diagnosis, biological samples and pharmaceutical compounds analysis.Progesterone is the predominant gestagen in most mammals studied so far. It plays a substantial role in the regulation of the female reproductive cycle and in providing support for pregnancy maintenance. Despite its known functions, gaps in knowledge are present regarding its reduced metabolites that potentially exert biological activity. Therefore, a new UHPLC-HRMS method based on a Q Exactive™ mass spectrometer was developed to detect and quantify simultaneously progesterone, its hormone precursor pregnenolone and 10 reduced progestogens (20α-DHP, 20β-DHP, 3α,5α-THP, 3α,5β-THP, 3β,5α-THP, 3β,5β-THP, 3α-DHP, 3β-DHP, 5α-DHP and 5β-DHP) in plasma and serum samples. Purification was achieved by an optimized solid phase extraction (SPE) and the analysis was conducted in positive electrospray ionization (ESI) mode with the application of multiplexed selected ion monitoring (msx-t-SIM). The method validation included the study of sensitivity, selectivity, curve fitting, carry-over, accuracy, precision, recovery and matrix effects. Despite the poor ionization properties of underivatized steroids, a high sensitivity in the range of pg/mL was achieved.Interference of the Schlieren effect on sea water analysis by spectrophotometry is caused by the flow of solutions of different ionic strengths through a flow cell. A flow injection assay protocol programmed in a flow-batch format removes this interference and allows the use of a calibration line, obtained in deionized water, for determination of analytes in sea water samples of different salinity. This Single Line Calibration (SLC) technique is validated on the most frequently performed nutrient assays. Automated determinations, performed at rates ranging from 20 to 60 samples/hr, covered seawater sample ranges from nM to mM with limits of detection 12 nM for nitrite, 94 nM for nitrate, 47 nM for phosphate, and 240 nM for silicate. Reproducibility of the determinations was equal to or better than, 3% r.s.d. and day to day calibration was within 10%. The programmable FI, uses about 1/5th volume of reagents compared to continuous flow techniques.Packed column SFC has become very popular for preparative and analytical separations due to the low cost of CO2, its accessible critical temperature, and pressure, with the additional benefit of a low environmental burden. Currently, there is a shortage of new polar stationary phase chemistries for SFC. In this work, two new functionalized cyclofructan columns are introduced and evaluated for their performance in achiral SFC separations for the first time. Cyclofructan (CF6), a macrocyclic oligosaccharide, was covalently linked with benzoic acid (BCF6) and propyl sulfonic acid (SCF6) groups by ether bonds. Superficially porous particles (2.7 μm) bonded with modified CF6 showed markedly different selectivity than native CF6. In SFC, peak shapes of amines and basic compounds are often compromised. We show that small quantities (~5.7% v/v) of water added to the methanol modifier in CO2 improves peak symmetries of primary, secondary, and tertiary amines. Efficiencies as high as 200,000 plates/m (reduced plate height ~ 1.8) were observed for benzamide and amitriptyline on the BCF6 column. The relative standard deviations (RSDs) of retention times on BCF6 were about 1.4%, and on SCF6 were less than 1%. Amines on the SCF6 column showed plate counts as high as 170,000 plates/m. Tetramethylammonium acetate is examined as an alternative to water in MeOH. A run time of 36 min with methanol, trifluoroacetic acid, triethylamine mobile phase was reduced to less then 5 min with complete baseline resolution for a set of amines. The new stationary phases allow greener approaches towards solving separation problems.A sensitive optical sensor based on hollow core microstructure optical fibers modified with deep eutectic solvent was produced for the first time. An easy procedure for the modification of hollow-core microstructure optical fibers with deep eutectic solvent was developed. Deep eutectic solvents based on natural monoterpenoids and fatty acids were investigated for glass surface modification. The sensor was used for the determination of non-steroidal anti-inflammatory drugs (mefenamic acid, diclofenac, flurbiprofen and ketoprofen) in human urine samples. The mechanism of the sensor response was investigated and discussed. Liquid-phase microextraction of non-steroidal anti-inflammatory drugs was implemented in deep eutectic solvent phase supported in the inner surface of hollow-core microstructure optical fibers followed by transmission spectra measurement in one analytical device. The preconcentration step performed directly in the analytical device allowed to obtain high sensitivity and selectivity. The limits of detection calculated from the calibration plots based on 3σ were 3 μg L-1 for all target analytes.The determination of palladium (Pd) in environmental samples by ICP-MS is challenging as all its isotopes are extensively interfered due to isobaric (e.g. 110Cd on 110Pd, 106Cd on 106Pd), polyatomic (e.g. 92Mo16O on 108Pd, 89Y16O on 105Pd) and doubly-charged (e.g. 208Pb2+ on 104Pd) species formed in the plasma from elements usually present at concentrations several orders of magnitude higher. As a result, the determination of Pd in natural waters is extremely scarce despite is has been proven that this metal is subject to a significant anthropogenic impact mainly linked to its use in catalytic converters in motor vehicles. In order to overcome this situation, we have developed an ultra-trace interference-free methodology for the determination of Pd in natural waters by ICP-MS after on-line matrix separation and preconcentration. The method is based on the strong affinity of Pd towards a commercially-available carboxymethylated polyethylenimine resin, which also has the ability to retain most of the transitioniming to improve our understanding of the behavior of Pd in natural waters.The quantification of Cr (VI) in the cement matrix is highly important, given the possibility of suffering illnesses including dermatitis, induced nasal carcinoma, and DNA damage produced by inhalation of and/or direct contact with this substance by construction workers. This study presents an analytical validation of the determination of water-soluble Cr (VI) using Ultraviolet-Visible Spectroscopy (UV-Vis) with 1.5-diphenylcarbazide. To do so, different performance characteristics were determined working interval, analytical sensitivity, linearity, limits of detection (LOD) and quantification (LOQ), as well as measurement uncertainty, in order to provide better metrological information about the performance of this method. The study also focused on evaluating the impact of use of different types of standard sands (ASTM C-778 and CEN) for preparing mortar cement and extracting water soluble Cr (VI) present in the cement. For this purpose, two cements with different concentrations (2.01 ± 0.21 and 0.75 ± 0.09 mg-kg-1) of Cr (IV) were created to evaluate extraction using three types of treatments oxidized with potassium peroxidisulfite, non-oxidized, and an alternative method using cement paste. It was observed that mortar cement using ASTM C-778 sand tends to underestimate Cr (IV) content when concentrations are below 0.8 mg kg-1, while at higher concentrations of ~2.0 mg kg-1 it does not generate different results compared to those obtained using mortar cement made with CEN-standard sand. An alternative method called "paste extraction" also showed statistically comparable results with respect to standard mortar for both concentration levels evaluated. Finally, samples of cement marketed in Costa Rica were analyzed using different types of water soluble Cr (IV) extraction methods. The results show concentrations between 0.70 ± 0.13 mg kg-1 and 1.30 ± 0.13 mg kg-1, demonstrating that they comply with the limits established by international standards and national regulations in Costa Rica.Lanthanide nanoprobes have attracted extensive attention for applications in cellular imaging and biological sensing. Herein, water-dispersible europium (III)-based (Eu(III)-based) nanoprobes were prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization-induced self-assembly (PISA) of hydrophobic monomers (Eu(III)-containing monomer and methyl methacrylate (MMA)) using hydrophilic macro-chain transfer agent poly(PEGMA)-CTA. The resulted poly(PMEu) nanoprobes showed spherical in shape in good monodispersity with average diameters of around 210 nm. The poly(PMEu) nanoprobles excellent aqueous dispersity, high aqueous stability and good luminescence properties with quantum yields of 37.21% and fluorescence lifetime of 312.4 μs. Moreover, the poly(PMEu) nanoprobes exhibited good cellular biocompatibility with cell viabilities of 88.2% and high fluorescence intensity for in vitro cellular imaging. The present approach provides a facile strategy for fabrication of luminescent Eu(III)-based nanoprobes with great potential applications for biological imaging.