Nanoparticle-based immunosensors and immunoassays for aflatoxins

Aflatoxins are naturally existing mycotoxins produced mainly by Aspergillus flavus and Aspergillus parasiticus, present in a wide range of food and feed products. Because of their extremely high toxicity and carcinogenicity, strict control of maximum residue levels of aflatoxins in foodstuff is set by many countries. In daily routine, different chromatographic methods are used almost exclusively. As supplement, in several companies enzyme immunoassay-based sample testing as primary screening is performed. Recently, nanomaterials such as noble metal nanoparticles, magnetic particles, carbon nanomaterials, quantum dots, and silica nanomaterials are increasingly utilized for aflatoxin determination to improve the sensitivity and simplify the detection. They are employed either as supports for the immobilization of biomolecules or as electroactive or optical labels for signal transduction and amplification. Several nanoparticle-based electrochemical, piezoelectric, optical, and immunodipstick assays for aflatoxins have been developed. In this review, we summarize these recent advances and illustrate novel concepts and promising applications in the field of food safety.     

Assessment of the surfactant-dye binding degree method as an alternative to the methylene blue method for the determination of anionic surfactants in aqueous environmental samples

The surfactant to dye binding degree (SDBD) method is proposed for the routine monitoring of anionic surfactants in aqueous environmental samples and their analytical features compared with those provided by the standard methylene blue (MB) method. This new analytical approach is based on the effect that anionic surfactants exert on the binding degree of the cationic surfactant didodecyldimethylammonium bromide (DDABr) to the anionic dye Coomassie Brilliant Blue G (CBBG). The formation of DDABr-CBBG aggregates is monitored photometrically. The analytical applicability of the proposed method was demonstrated by determining anionic surfactants in tap, river and swamp water, and raw and treated sewage. The mean recoveries obtained ranged between 99 and 101%. The SDBD method offers important advantages over the classical MB method: it is more sensitive, selective, precise, simple and rapid; the analytical response is independent of the molecular structure of the anionic surfactants, and the volume of sample required for analysis and the consumption of organic solvents are significantly reduced.     

漆树漆酶的催化氧化作用 (ⅹⅢ)──Fe~(2+)离子对漆酶催化氧化反应的影响()

以５,６－二溴－２,３－二氰基氢醌为底物,在ｐＨ４．５０条件下,用分光光度法考察了ＦｅＳＯ４对漆树漆酶催化氧化反应的影响．结果表明,在本文实验条件下ＳＯ２－４离子对酶促反应的影响基本可以忽略,而Ｆｅ２＋离子对漆酶的催化氧化反应则有明显的竞争性抑制作用．研究证实,Ｆｅ２＋离子的抑制作用是通过它还原酶促反应的产物半醌自由基阴离子来实现的     

Thermodynamics, Conformation and Active Sites of the Binding of Zn–Nd Hetero-bimetallic Schiff Base to Bovine Serum Albumin

The interactions between N,N′-di(2-hydroxy-3-methyoxy-phenyl-1-methylene)-o-phenyldiamine-mone Zn(II), Nd(III) nitrate (2LZnNd) and bovine serum albumin (BSA) was investigated by various spectroscopic techniques under physiological conditions. It was proved that the fluorescence quenching of BSA by 2LZnNb was a result of the formation of a non-fluorescent complex with the binding constants of 3.15 × 10⁵; 2.72 × 10⁵ and 2.44 × 10⁵ M^–1 at 298 K, 304 K and 310 K, respectively. A marked increase in the fluorescence anisotropy in the proteinous environments indicates that BSA introduces motional restriction on the drug molecule. The corresponding thermodynamics parameters ΔH and ΔS were calculated to be –16.36 kJ mol^–1 and 43.48 J mol^–1 K^–1 via van’t Hoff equation. Moreover, the competitive probes experiment revealed that the binding location of 2LZnNb to BSA is in the hydrophobic pocket of site II. The effect of 2LZnNb on the conformation of BSA has been analyzed by means of CD spectrum and three-dimensional fluorescence spectra. The results indicate that the conformation of BSA molecules was changed in the presence of 2LZnNb Schiff base.     

Enantioseparation of flurbiprofen on amylose-derived chiral stationary phase by supercritical fluid chromatography

The separation of the enantiomers of flurbiprofen on an amylose-derived chiral stationary phase, Chiralpak AD-H, by supercritical fluid chromatography (SFC) under both linear and non-linear conditions is studied. Pulse injections were implemented using supercritical CO₂modified with methanol as a mobile phase at a temperature of 30 °$°$C. At linear conditions, the isotherm is determined directly from the chromatogram. Under overload conditions, the elution profiles were described by competitive Langmuir and bi-Langmuir isotherm. Isotherm parameters were estimated using the inverse method and the effects of operation variables such as pressure and modifier composition were studied. The value of selectivity is from 1.9 to 2.1 while the value of resolution is from 5.3 to 11.8. The number of theoretical plates is always greater than 5000 indicating high efficiency of SFC.     

Kinetic study of uranium speciation in model solutions and in natural waters using Competitive Ligand Exchange Method

Kinetic speciation of uranium in model solutions containing uranium and humic acid (HA) and in natural waters has been investigated by Competitive Ligand Exchange Method (CLEM). In alkaline freshwaters, most of uranium species were uranium-carbonate species, which were labile in the CLEM experiment. The uranium speciation of every sample was characterized either as “labile” or “non-labile” uranium complexes depending on the dissociation rate coefficients of the complexes. The results showed that as the U(VI)/HA ratio was decreased, the dissociation rate coefficients decreased and the labile fraction decreased as well. When the U(VI)/HA ratio was 0.1, the labile fraction of the U(VI)-HA increased with increasing pH; however, there was no pH effect on the dissociation of U(VI)-HA complexes at lower U(VI)/HA ratios. Chelex-100 had some limitations in its use for the study of dissociation of U(VI)-HA complex at very low U(VI)/HA ratios. By developing an analytical method and procedure for quantitative determination of kinetic parameters for the dissociation of uranium-HA complexes in model solutions and natural waters, this work has made a substantial contribution to analytical chemistry.     

Electrochemical evidence of self-substrate inhibition as functions regulation for cellobiose dehydrogenase from Phanerochaete chrysosporium

The reaction mechanism of cellobiose dehydrogenase (CDH) from Phanerochaete chrysosporium, adsorbed on graphite electrodes, was investigated by following its catalytic reaction with cellobiose registered in both direct and mediated electron transfer modes between the enzyme and the electrode. A wall-jet flow through amperometric cell housing the CDH-modified graphite electrode was connected to a single line flow injection system. In the present study, it is proven that cellobiose, at concentrations higher than 200 μM, competes for the reduced state of the FAD cofactor and it slows down the transfer of electrons to any 2e⁻/H⁺ acceptors or further to the heme cofactor, via the internal electron transfer pathway. Based on and proven by electrochemical results, a kinetic model of substrate inhibition is proposed and supported by the agreement between simulation of plots and experimental data. The implications of this kinetic model, called pseudo-ping-pong mechanism, on the possible functions CDH are also discussed. The enzyme exhibits catalytic activity also for lactose, but in contrast to cellobiose, this sugar does not inhibit the enzyme. This suggests that even if some other substrates are coincidentally oxidized by CDH, however, they do not trigger all the possible natural functions of the enzyme. In this respect, cellobiose is regarded as the natural substrate of CDH.     

Competitive facility location on decentralized supply chains

This paper addresses a novel competitive facility location problem about a firm that intends to enter an existing decentralized supply chain comprised of three tiers of players with competition: manufacturers, retailers and consumers. It first proposes a variational inequality for the supply chain network equilibrium model with production capacity constraints, and then employs the logarithmic-quadratic proximal prediction–correction method as a solution algorithm. Based on this model, this paper develops a generic mathematical program with equilibrium constraints for the competitive facility location problem, which can simultaneously determine facility locations of the entering firm and the production levels of these facilities so as to optimize an objective. Subsequently, a hybrid genetic algorithm that incorporates with the logarithmic-quadratic proximal prediction–correction method is developed for solving the proposed mathematical program with an equilibrium constraint. Finally, this paper carries out some numerical examples to evaluate proposed models and solution algorithms.     

Evolutionary model of the growth and size of firms

The key idea of this model is that firms are the result of an evolutionary process. Based on demand and supply considerations the evolutionary model presented here derives explicitly Gibrat’s law of proportionate effects as the result of the competition between products. Applying a preferential attachment mechanism for firms, the theory allows to establish the size distribution of products and firms. Also established are the growth rate and price distribution of consumer goods. Taking into account the characteristic property of human activities to occur in bursts, the model allows also an explanation of the size–variance relationship of the growth rate distribution of products and firms. Further the product life cycle, the learning (experience) curve and the market size in terms of the mean number of firms that can survive in a market are derived. The model also suggests the existence of an invariant of a market as the ratio of total profit to total revenue. The relationship between a neo-classic and an evolutionary view of a market is discussed. The comparison with empirical investigations suggests that the theory is able to describe the main stylized facts concerning the size and growth of firms.