Automated analysis of lidocaine and its metabolite in plasma by in-tube solid-phase microextraction coupled with LC-UV for pharmacokinetic study

A sensitive, selective, and reproducible in-tube solid-phase microextraction and liquid chromatographic (in-tube SPME/LC-UV) method for determination of lidocaine and its metabolite monoethylglycinexylidide (MEGX) in human plasma has been developed, validated, and further applied to pharmacokinetic study in pregnant women with gestational diabetes mellitus (GDM) subjected to epidural anesthesia. Important factors in the optimization of in-tube SPME performance are discussed, including the draw/eject sample volume, draw/eject cycle number, draw/eject flow rate, sample pH, and influence of plasma proteins. The limits of quantification of the in-tube SPME/LC method were 50 ng/mL for both metabolite and lidocaine. The interday and intraday precision had coefficients of variation lower than 8%, and accuracy ranged from 95 to 117%. The response of the in-tube SPME/LC method for analytes was linear over a dynamic range from 50 to 5000 ng/mL, with correlation coefficients higher than 0.9976. The developed in-tube SPME/LC method was successfully used to analyze lidocaine and its metabolite in plasma samples from pregnant women with GDM subjected to epidural anesthesia for pharmacokinetic study.     

Adsorption of bovine serum albumin on template-polymerized chitosan/poly(methacrylic acid) complexes

Particulate systems composed of polyelectrolyte complexes (PEC) based on chitosan and poly(methacrylic acid) were obtained via template polymerization. The resultant particles were characterized as having regions with different charge densities: chitosan predominating in the core and poly(methacrylic acid) at the surface, the particles being negatively charged, as a consequence. Albumin was adsorbed on these particles (after cross-linking with glutardialdehyde), and pH was controlled to obtain two conditions: (i) adsorption of positively charged albumin and (ii) adsorption of albumin at its isoelectric point. Adsorption isotherms and zeta-potential measurements showed that albumin adsorption was controlled by hydrogen bonding/van der Waals interactions and that brush-like structures may enhance the adsorption of albumin on these particles. It was also found that shearing can induce desorption of albumin from the PEC surface, depending on the continuous phase albumin concentration.     

Acid character control of bioactive glass/polyvinyl alcohol hybrid foams produced by sol–gel

Bioactive glass/polymer hybrids are promising materials for biomedical applications because they combine the bioactivity of bioceramics with the flexibility of polymers. In previous work hybrid foams with 80% bioactive glass and 20% polyvinyl alcohol were prepared by the sol–gel method. The produced hybrids presented a high acidic character due to the catalysts added. In this work different methods to control the acidity and toxicity of the hybrids were also evaluated, through changes in the synthesis pH and use of different neutralization solutions. The hybrids were prepared with inorganic phase composition of 70%SiO₂–30%CaO and PVA fractions of 20–60% by the sol–gel method. The characterization of the obtained foams was done by FTIR, SEM, Raman Spectroscopy, Helium Picnometry and TGA. The immersion of hybrids in a calcium acetate solution was the most adequate neutralization method. The foams presented porosity of 60–85% and pore diameters of 100–500 μm with interconnected structure.     

Colouring Clique-Hypergraphs of Circulant Graphs

A clique-colouring of a graph G is a colouring of the vertices of G so that no maximal clique of size at least two is monochromatic. The clique-hypergraph, ${\mathcal{H}(G)}$ , of a graph G has V(G) as its set of vertices and the maximal cliques of G as its hyperedges. A vertex-colouring of ${\mathcal{H}(G)}$ is a clique-colouring of G. Determining the clique-chromatic number, the least number of colours for which a graph G admits a clique-colouring, is known to be NP-hard. In this work, we establish that the clique-chromatic number of powers of cycles is equal to two, except for odd cycles of size at least five, that need three colours. For odd-seq circulant graphs, we show that their clique-chromatic number is at most four, and determine the cases when it is equal to two. Similar bounds for the chromatic number of these graphs are also obtained.     

Comparative Analysis of the Distribution of Copper in Green and Brown Brazilian Propolis Extracts

We proposed here a novel analytical procedure for copper speciation in green and brown propolis extracts using SEC—HPLC—GFAAS with 0.5% m v^?1 SDS in 2.5 m mol L^?1 Tris–HCl (pH 7.4) as the mobile phase buffer solution. Both basic (0.05 mol L^?1 NaOH) and acid (0.05 mol L^?1 HCl) conditions were evaluated for sample extraction. Depending on the extraction procedure, differences in copper distribution were identified. Copper was mainly associated with high-molecular-weight (HMW) fractions in green propolis extract when extracted with basic solution, whereas with acid extraction solution, only low-molecular-weight (LMW) fractions were obtained in both samples. Furthermore, combined analysis of results obtained using SEC-UV and GF AAS confirmed the association of copper with LMW and HMW species.     

Highly Selective Water Adsorption in a Lanthanum Metal–Organic Framework

We present a new metal–organic framework (MOF) built from lanthanum and pyrazine‐2,5‐dicarboxylate (pyzdc) ions. This MOF, [La(pyzdc)_1.5(H₂O)₂] ? 2 H₂O, is microporous, with 1D channels that easily accommodate water molecules. Its framework is highly robust to dehydration/hydration cycles. Unusually for a MOF, it also features a high hydrothermal stability. This makes it an ideal candidate for air drying as well as for separating water/alcohol mixtures. The ability of the activated MOF to adsorb water selectively was evaluated by means of thermogravimetric analysis, powder and single‐crystal X‐ray diffraction and adsorption studies, indicating a maximum uptake of 1.2 mmol g^?1 MOF. These results are in agreement with the microporous structure, which permits only water molecules to enter the channels (alcohols, including methanol, are simply too large). Transient breakthrough simulations using water/methanol mixtures confirm that such mixtures can be separated cleanly using this new MOF.     

Solid-state C NMR and molecular modeling studies of acetyl aleuritolic acid obtained from Croton cajucara Benth

Solid-state ¹³C nuclear magnetic resonance (¹³C NMR) with magic-angle spinning (MAS) and with cross-polarization and magic-angle spinning (CP/MAS) spectra, and differential scanning calorimetry (DSC) techniques were used to obtain structural data from a sample of acetyl aleuritolic acid (AAA) extracted from the stem bark of Croton cajucara Benth. (Euphorbiaceae) and recrystallized from acetone. Since solid-state ¹³C NMR results suggested the presence of more than one molecule in the unitary cell for the AAA, DSC analysis and molecular modeling calculations were used to access this possibility. The absence of phase transition peaks in the DSC spectra and the dimeric models of AAA simulated using the semi-empirical PM3 method are in agreement with that proposal.     

Simultaneous determination of eight pesticide residues in coconut using MSPD and GC/MS

A simple and effective extraction method based on matrix solid-phase dispersion (MSPD) was developed to determine dimethoate, malathion, lufenuron, carbofuran, 3-hydroxycarbofuran, thiabendazole, difenoconazole and trichlorfon in coconut pulp using gas chromatography-mass spectrometry with selected ion monitoring (GC/MS, SIM). Different parameters of the method were evaluated, such as type of solid-phase (C(18), alumina, silica-gel and Florisil), the amount of solid-phase and eluent (dichloromethane, acetone, ethyl acetate, acetonitrile, n-hexane and n-hexane:ethyl acetate (1:1, v/v)). The best results were obtained using 0.5 g of coconut pulp, 1.0 g of C(18) as dispersant sorbent, 1.0 g of Florisil as clean-up sorbent and acetonitrile saturated with n-hexane as eluting solvent. The method was validated using coconut pulp samples fortified with pesticides at different concentration levels (0.25-1.0 mg kg(-1)). Average recoveries (four replicates) ranged from 70.1% to 98.7%, with relative standard deviations between 2.7% and 14.7%, except for lufenuron and difenoconazole, for which recoveries were 47.2% and 48.2%, respectively. Detection and quantification limits for coconut pulp ranged from 0.02 to 0.17 mg kg(-1) and from 0.15 to 0.25 mg kg(-1), respectively.     

Application of a dipping procedure to construct a241Am skull phantom

The construction of reliable bone phantoms to calibrate whole body counting facilities for bone-seeking radionuclides has been a challenge for several research institutes. Different techniques have been applied to get uniform distribution of those nuclides in bone tissue. A²⁴¹Am skull phantom was developed at the Institute of Radiation Protection and Dosimetry/Brazilian Nuclear Energy Commission's (IRD/CNEN) Whole Body Counting facility, using a dipping procedure. Preliminary tests were performed using non-radioactive ink solution. The first step was to choose the appropriate solvent to be used, since it was observed that acid solutions attack bone tissue. At the second step, pieces of skull were dipped into those solutions to check the extent and homogeneity of the penetration. The third step consisted of verifying the dipping time using a²⁴¹Am standard solution. The homogeneity was checked with a high-purity germanium detector. Tissue-equivalent material was used to cover the skull surface and to simulate the low energy X and gamma radiation attenuation. The calibration factor and the detection limit were calculated for two phoswich detectors positioned at each side of the head, which is the standard geometry for this kind of measurement.