Application of direct-injection detector integrated with the multi-pumping flow system to chemiluminescence determination of the total polyphenol index

In this work, we present a novel chemiluminescence (CL) method based on direct-injection detector (DID) integrated with the multi-pumping flow system (MPFS) to chemiluminescence determination of the total polyphenol index. In this flow system, the sample and the reagents are injected directly into the cone-shaped detection cell placed in front of the photomultiplier window. Such construction of the detection chamber allows for fast measurement of the CL signal in stopped-flow conditions immediately after mixing the reagents. The proposed DID-CL-MPFS method is based on the chemiluminescence of nanocolloidal manganese(IV)-hexametaphosphate-ethanol system. The application of ethanol as a sensitizer, eliminated the use of carcinogenic formaldehyde. Under the optimized experimental conditions, the chemiluminescence intensities are proportional to the concentration of gallic acid in the range from 5 to 350 ng mL⁻¹. The DID-CL-MPFS method offers a number of advantages, including low limit of detection (0.80 ng mL⁻¹), high precision (RSD = 3.3%) and high sample throughput (144 samples h⁻¹) as well as low consumption of reagents, energy and low waste generation. The proposed method has been successfully applied to determine the total polyphenol index (expressed as gallic acid equivalent) in a variety of plant-derived food samples (wine, tea, coffee, fruit and vegetable juices, herbs, spices).     

Comparison of geometric, electronic, and vibrational properties for isomers of small fullerenes C20-C36

We employ the self-consistent-charge density-functional tight-binding (SCC-DFTB) method for computing geometric, electronic, and vibrational properties for various topological isomers of small fullerenes. We consider all 35 five- and six-member rings containing isomers of small fullerenes, C20, C24, C26, C28, C30, C32, C34, and C36, as first part of a larger effort to catalog CC distance distributions, valence CCC angle distributions, electronic densities of states (DOSs), vibrational densities of states (VDOSs), and infrared (IR) and Raman spectra for fullerenes C20-C180. Common features among the fullerenes are identified and properties characteristic for each specific fullerene isomer are discussed.     

Enhancement of the Antioxidant and Skin Permeation Properties of Betulin and Its Derivatives

This study investigated the antioxidant activity DPPH, ABTS, and Folin–Ciocalteu methods of betulin (compound 1) and its derivatives (compounds 2–11). Skin permeability and accumulation associated with compounds 1 and 8 were also examined. Identification of the obtained products (compound 2–11) and betulin isolated from plant material was based on the analysis of ¹H- NMR and ¹³C-NMR spectra. The partition coefficient was calculated to determine the lipophilicity of all compounds. In the next stage, the penetration through pig skin and its accumulation in the skin were evaluated of ethanol vehicles containing compound 8 (at a concentration of 0.226 mmol/dm³), which was characterized by the highest antioxidant activity. For comparison, penetration studies of betulin itself were also carried out. Poor solubility and the bioavailability of pure compounds are major constraints in combination therapy. However, we observed that the ethanol vehicle was an enhancer of skin permeation for both the initial betulin and compound 8. The betulin 8 derivative showed increased permeability through biological membranes compared to the parent betulin. The paper presents the transformation of polycyclic compounds to produce novel derivatives with marked antioxidant activities and as valuable intermediates for the pharmaceutical industry. Moreover, the compounds contained in the vehicles, due to their mechanism of action, can have a beneficial effect on the balance between oxidants and antioxidants in the body, minimizing the effects of oxidative stress. The results of this work may contribute to knowledge regarding vehicles with antioxidant potential. The use of vehicles for this type of research is therefore justified.     

Assessment of the Effectiveness of Rehabilitation after Total Knee Replacement Surgery Using Sample Entropy and Classical Measures of Body Balance

Exercises in virtual reality (VR) have recently become a popular form of rehabilitation and are reported to be more effective than a standard rehabilitation protocol alone. The aim of this study was to assess the efficacy of adjunct VR training in improving postural control in patients after total knee replacement surgery (TKR). Forty-two patients within 7–14 days of TKR were enrolled and divided into a VR group and a control group (C). The C group underwent standard postoperative rehabilitation. The VR group additionally attended twelve 30-min exercise sessions using the Virtual Balance Clinic prototype system. Balance was assessed on the AMTI plate in bipedal standing with and without visual feedback before and after the four-week rehabilitation. Linear measures and sample entropy of CoP data were analyzed. After four weeks of rehabilitation, a significant reduction in parameters in the sagittal plane and ellipse area was noted while the eyes remained open. Regression analysis showed that sample entropy depended on sex, body weight, visual feedback and age. Based on the sample entropy results, it was concluded that the complexity of the body reaction had not improved. The standing-with-eyes-closed test activates automatic balance mechanisms and offers better possibilities as a diagnostic tool.     

The comparison of two column classification systems during the chromatographic analysis of steroids

Nowadays, due to the availability of hundreds of brands of reversed-phase liquid chromatographic columns, the selection of suitable columns can be difficult. Therefore, a good characterization and classification system is very important. Among published papers, the classification system based on quantitative structure-retention relationships and a method developed at the Katholieke Universiteit Leuven also exist. In quantitative structure-retention relationships, retention is evaluated in terms of the chemical structure of the analytes and the physicochemical properties of both the stationary and mobile phase. The second system allows to rank columns due to the values of four parameters and the calculation of specific F(KUL)-values for a reference column and to be compared with others. In this paper, the classification systems based both on quantitative structure-retention relationships and the F(KUL)-values using principal components analysis were compared. Moreover, the proposed column ranking systems have been checked in clinical practice case considering liquid chromatography determination of six steroid hormones in urine samples. Despite that the matching of both methods is not exactly the same, both classification systems provide simple, reliable and comparable results.     

Cadmium and lead recovery from yeast biomass

Properties of metal solution, environmental conditions and the type of biomaterials (microorganism genus, species or even strain) influence the mechanism of metal biosorption and consequently metal adsorption capacity, affinity and specificity. Cell surface properties determine the metal-microorganism interactions to a large extent. In this work the relationship between yeast surface properties and yeast’s ability to bind cadmium, lead and copper was studied. Surface charge and hydrophobicity before and after biosorption were determined using dye retention and solvent partition assays, respectively. There were differences in the surface charge and relative hydrophobicity among different yeast strains. A higher metal adsorption capacity for more negatively charged yeast cells was observed. Biosorption of heavy metals resulted in modifications to the surface charge and hydrophobicity of yeast cells. However, there were not statistically significant changes in the yeast surface charge and hydrophobicity after binding of heavy metals depending on the nature of the metal, initial metal concentration and solution pH.     

Preparation and characterization of polypyrrole with dispersed metallic rhodium particles

Polypyrrole (PPy) with dispersed metallic Rh particles has been prepared by all‐chemical route, i.e. reduction of Rh³⁺ ions existing in RhCl₃ aqueous solutions with sodium borohydride (NaBH₄) carried out in the presence of the previously obtained PPy doped with chloride ions (PPyCl). PPy–Rh composites thus formed have been characterized using X‐ray diffraction (XRD), scanning and transmission electron microscopies (SEM, TEM) combined with energy dispersive X‐ray (EDX) microanalysis, Rh3d X‐ray photoelectron (XPS), and IR spectroscopies. This has made it possible to find out that metallic Rh nanoparticles, mainly of sizes below 10 nm, have been present in the composites. Agglomerates, with sizes up to 0.7 µm, have been formed in the systems containing higher amounts of Rh. PPy serving as the matrix in the composites has been doped. However, its doping level has been lower than that of the starting PPyCl. This has been explained by partial reduction of the polymer occurring during preparation of the composites. Catalytic properties of the PPy–Rh systems have been investigated using isopropyl alcohol conversion as a test reaction. It has been established that the composites are active redox catalysts. This makes them promising materials for applications as catalysts of various redox processes. Copyright © 2010 John Wiley & Sons, Ltd.