Quantification of L‐ergothioneine in whole blood by hydrophilic interaction ultra‐performance liquid chromatography and UV‐detection

A new hydrophilic interaction ultra‐performance LC method was established for the whole blood measurement of L‐ergothioneine. Chromatographic separation was achieved in a fairly short time, less than 4 min, on a 100 × 2.1 mm Acquity UPLC BEH HILIC 1.7 μm column with a mobile phase consisting of a mixture of 100 mmol/L ammonium acetate/ACN/water (5:85:10, v/v/v) that flowed isocratically at 0.250 mL/min. The LOD and the limit of quantification were 3.85 and 11.67 μmol/L, respectively. The method exhibited linearity in a concentration range of 15.63–1000 μmol/L (R² > 0.999). Mean recovery was 96.34% whereas intraassay and interassay precision were 1.52 and 1.82% RSD, respectively. On the whole, the developed method is simple, fast, precise, accurate, and sensitive and may be useful for routine analyses.     

Determination of creatinine in human serum by short-end injection capillary zone electrophoresis

A new ultra-rapid free-solution capillary zone electrophoresis method to measure serum creatinine is presented. Procedural parameters such as injection mode, concentration and pH of phosphate running buffer and acidic deproteinization of serum samples were investigated. Short-end injection permits a decrease of the analysis time by injecting samples at the outlet end of a silica capillary closest to the detection window, so reducing the migration distance. Thus, when a capillary with an effective length of 10.2 cm and a 40 mmol/L sodium phosphate buffer pH 2.35 was used, the obtained migration time of the creatinine peak was the shortest never described before, about 1.1 min. These conditions give a good reproducibility of the migration times (coefficient of variation, CV% < 0.5) and the peak areas (CV% < 2.8). Intra- and interassay CV were 3.06 and 6.26%, respectively, and analytical recovery was 99.4%. We compared our proposed method to Jaffé colorimetric assay, by measuring serum creatinine in 128 normal subjects. The obtained data were analyzed by the Passing and Bablok regression and Bland-Altman test. Creatinine concentration in healthy subjects was also used to investigate on its relationships with plasma thiols levels.     

An exact algorithm to extend lifetime through roles allocation in sensor networks with connectivity constraints

We face the problem of scheduling optimally the activities in a wireless sensor network in order to ensure that, in each instant of time, the activated sensors can monitor all points of interest (targets) and route the collected information to a processing facility. Each sensor is allocated to a role, depending on whether it is actually used to monitor the targets, to forward information or kept idle, leading to different battery consumption ratios. We propose a column generation algorithm that embeds a highly efficient genetic metaheuristic for the subproblem. Moreover, to optimally solve the subproblem, we introduce a new formulation with fewer integer variables than a previous one proposed in the literature. Finally, we propose a stopping criterion to interrupt the optimal resolution of the subproblem as soon as a favorable solution is found. The results of our computational tests show that our algorithm consistently outperforms previous approaches in the literature, and also improves the best results known to date on some benchmark instances.     

Field-amplified online sample stacking capillary electrophoresis UV detection for plasma malondialdehyde measurement

Malondialdehyde (MDA) determination is the most widely used method for monitoring lipid peroxidation. Here, we describe an easy field-amplified sample injection (FASI) CE method with UV detection for the detection of free plasma MDA. MDA was detected within 8 min by using 200 mmol/L Tris phosphate pH 5.0 as running buffer. Plasma samples treated with ACN for protein elimination were directly injected on capillary without complex cleanup and/or sample derivatization procedures. Using electrokinetic injection, the detection limit in real sample was 3 nmol/L, thus improving of about 100-fold the LOD of the previous described methods based on CE. Precision tests indicate a good repeatability of our method both for migration times (CV = 1.11%) and for areas (CV = 2.05%). Moreover, a good reproducibility of intra- and inter-assay tests was obtained (CV = 2.55% and CV = 5.14%, respectively). Suitability of the method was tested by measuring MDA levels in 44 healthy volunteers.     

A novel LIF-CE method for the separation of hyaluronan- and chondroitin sulfate-derived disaccharides: Application to structural and quantitative analyses of human plasma low- and high-charged chondroitin sulfate isomers

The report describes a rapid and simple CE method using LIF detection for the analysis of unsaturated disaccharides obtained from enzymatic depolymerization of plasma chondroitin sulfate (CS) isomers. The disaccharide reducing groups were labeled with 2-aminoacridone (AMAC). The fluorotagged products can be separated by reversed-polarity CE using a sodium acetate buffer, pH 3.8, in the presence of 0.05% methylcellulose. The choice of the appropriate electrophoretic conditions was performed after a deep analysis of the most important parameters affecting analyte separation. In particular, the effect of both run buffer concentration and pH on resolution, efficiency, migration times, and peak area was evaluated. The selected electrophoretic conditions allowed us to separate the CS isomers-derived Delta-disaccharides in less than 12 min, also resolving the nonsulfated disaccharides released from CS isomers from those released from hyaluronan (HA). Moreover, these conditions gave a good reproducibility of both the migration times (CV%, 0.25) and the peak areas (CV%, 1.4). Intra- and interassay CV were 5.37 and 7.23%, respectively, and analytical recovery was about 86%. The applicability of the above method to the quantitative and structural disaccharide analyses of plasma CS isomers was investigated. Data obtained from 44 healthy human subjects were compared with those obtained by a fluorophore-assisted carbohydrate electrophoresis (FACE) reference assay, by using the Passing and Bablok regression and Bland-Altman tests. The developed method could represent a good tool for an ultrasensitive analysis of CS isomers in biological samples from different sources, particularly when samples are available in very low amounts.     

Improved rapid assay of plasma uric acid by short-end injection capillary zone electrophoresis

A rapid and simple short-end injection capillary zone electrophoresis method was developed for the quantification of plasma uric acid. The separation was performed in an uncoated fused-silica capillary (50 μm ID, 60 cm total length, 10.2 cm effective length) by using as a background electrolyte a 75 mmol/L glycylglycine solution titrated with NaOH 5 mol/L to pH 9.0, a voltage of 28 kV, a cartridge temperature of 15 °C, and direct UV detection at 292 nm. Under optimized conditions, uric acid was determinate in little more than 1 min (1.076 minutes). In order to verify the accuracy of the analysis, urate levels were measured in 543 apparently healthy volunteers by the new assay and our previous method, and the obtained data were compared by Passing–Bablock regression, Bland–Altman test, and a new regression-based approach, which showed a good agreement between two methods.     

Synthesis and characterizations of Ho2O3 modified SrBi2Nb2O9 ceramics

SrBi_2-xHo_xNb₂O₉ (0?≤?x?≤?0.5) ceramics were prepared through the conventional solid state route. The materials have been characterized by XRD, FTIR and SEM. All compounds were pure and well crystallized. In FTIR spectroscopy, the spectral patterns of the crystal structures of these polyphases are unique and smoothly different from each other. The grains were prone to become spherical with increasing x. Dielectric and electrical properties of these materials as a function of temperature at different frequencies have been carried out. The dielectric constant and dielectric loss were found to decrease with an increase of the holmium concentration at room temperature. Reaching up to x?=?0.4 and x?=?0.5, the diffusivity increases, leading to the occurrence of relaxor behavior. 20–30 at.% Ho doping on the Bi-site can fill up the oxygen vacancies and decrease the AC conductivity. However, at higher doping levels greater than 40% holmium oxide, the AC conductivity is found to increase.     

Synthesis,structural and dielectric properties of SrBi<Subscript>2 – <Emphasis Type="Italic">x</Emphasis></Subscript>Sm<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Nb<Subscript>2</Subscript>O<Subscript>9</Subscript>

The SrBi_{2 – x} Sm _x Nb₂O₉ (x = 0, 0.4, 0.5) structure were synthesized by a conventional solid-state method. The X-ray diffraction shows an orthorhombic at room temperature. Dielectric constant, loss tangent and Ac conductivity of Sm-doped SrBi₂Nb₂O₉ were carried out, as well. A higher concentration of samarium (x = 0.4 and 0.5) doping leads to a significant reduction in dielectric constant and in Curie temperature. Rather relaxor type of behaviour took place.