A modified analytical method for total antioxidant potential assay using RP-HPLC with electrochemical detection and its application for pro- and antioxidative properties of dopamine measurement

Total antioxidant potential (TAP) is usually measured using photometric or fluorometric assays. Preliminary results of a reversed-phase high-performance liquid chromatography--electrochemical detection assay are given. The method is based on the generation of hydroxyl radicals in a Fenton reaction and analysis of the product of their interaction with p-hydroxybenzoic acid (3,4-dihydroxybenzoic acid). The method is applied to estimate the TAP of dopamine. As a result, depending on the concentration, dopamine is pro- or antioxidant. The results are compared with TAP measurements using a standard photometric method.     

Structural characterization of the intra- and inter-repeat copper binding modes within the N-terminal region of "prion related protein" (PrP-rel-2) of zebrafish

The unique biology of prion proteins (PrPs) allied with the public-health risks posed by prion zoonoses, such as various animal neurodegenerations, has focused much attention on the molecular basis of the controls cross-species and on the similarities between PrPs from different species. Given the common feature of PrPs as Cu(2+) binding proteins, it appears relevant to compare the impact of Cu(2+) on the stability constants and structures of "physiological" complexes. After having comprehensively delineated the interaction of Cu(2+) with mammalian and avian PrPs, the stabilities and molecular structures of species generated by Cu(2+) interacting with the irregular repeated domain derived from Danio rerio zebrafish PrP-rel-2 were investigated. Copper complexes with different zebrafish PrP-rel-2 fragments were analyzed by potentiometric and spectroscopic techniques. The data were interpreted as to provide evidence of all investigated repeat units selectively binding Cu(2+) via the His imidazole(s). The structural models obtained from paramagnetic NMR showed an intra- or inter-copper binding according to the number of the His in the sequence. In comparison to the mammalian and avian cases, the enzymatic function referred to SOD-like activity was shown to be rather faint in the fish PrPs cases.     

The ArNe-N2O van der Waals trimer: a high resolution spectroscopic study of its rotational spectrum,structure and dynamics

A new ternary van der Waals complex of the type rare gas-rare gas'-linear molecule, ArNe-N₂O, was investigated using a pulsed molecular beam cavity Fourier transform microwave spectrometer. The rotational spectra of six isotopomers of the trimer were studied in detail. These include Ar²⁰Ne-¹⁴N¹⁴NO, Ar²²Ne-¹⁴N¹⁴NO, Ar²⁰Ne-15N¹⁴NO, Ar²²Ne-¹⁵N¹⁴N0, Ar²⁰Ne-¹⁴N¹⁵NO and Ar²²Ne-¹⁴N¹⁵NO. Nuclear quadrupole hyperfine structures of the rotational transitions that are due to the one or two ¹⁴N nuclei were resolved and analysed. The resulting spectroscopic constants were used to provide structural and dynamical information about the trimer. Based on the quartic centrifugal distortion constants, a harmonic force field analysis was performed to estimate the frequencies of the van der Waals vibrational modes. A perturbation of the electronic charge distribution at the site of the central ¹⁴N nucleus of N²0 upon complex formation was detected and discussed. Differences of structural parameters of the trimer as compared to those of the respective dimer units are indicative of the presence of significant three-body non-additive contributions to the interaction energy.     

Robust chaos synchronization based on adaptive fuzzy delayed feedback ${\bf{\mathcal{H}}}_{\bf{\infty}}$ control

In this paper, we propose a new adaptive H_￥\mathcal H_\infty synchronization strategy, called an adaptive fuzzy delayed feedback H_￥\mathcal H_\infty synchronization (AFDFHS) strategy, for chaotic systems with uncertain parameters and external disturbances. Based on Lyapunov–Krasovskii theory, Takagi–Sugeno (T–S) fuzzy model and adaptive delayed feedback H_￥\mathcal H_\infty control scheme, the AFDFHS controller is presented such that the synchronization error system is asymptotically stable with a guaranteed H_￥\mathcal{H}_{\infty } performance. It is shown that the design of the AFDFHS controller with adaptive law can be achieved by solving a linear matrix inequality (LMI), which can be easily facilitated by using some standard numerical packages. An illustrative example is given to demonstrate the effectiveness of the proposed AFDFHS approach.     

Experimental parameters of vanadium determination by atomic-absorption spectroscopy with graphite-furnace atomization

It was found that impregnation of a graphite cuvette (HGA-72) with salts of elements which form stable carbides (Ta, Si Nb, Zr, W, La) decreases the absorbance signal for vanadium. The slope of the atomization curves indicates that formation of vanadium atoms is inhibited, probably by formation of a ternary compound between the impregnating element, vanadium and graphite. On the contrary bigger signals and better repeatability of results may be achieved when the cuvette is coated with pyrolytic graphite and methane is added to the sheath gas. The presence of methane increases the atomization efficiency and compensates for the disadvantageous influence of any air present in the sheath gas.     

Hybrid Drugs—A Strategy for Overcoming Anticancer Drug Resistance?

Despite enormous progress in the treatment of many malignancies, the development of cancer resistance is still an important reason for cancer chemotherapy failure. Increasing knowledge of cancers’ molecular complexity and mechanisms of their resistance to anticancer drugs, as well as extensive clinical experience, indicate that an effective fight against cancer requires a multidimensional approach. Multi-target chemotherapy may be achieved using drugs combination, co-delivery of medicines, or designing hybrid drugs. Hybrid drugs simultaneously targeting many points of signaling networks and various structures within a cancer cell have been extensively explored in recent years. The single hybrid agent can modulate multiple targets involved in cancer cell proliferation, possesses a simpler pharmacokinetic profile to reduce the possibility of drug interactions occurrence, and facilitates the process of drug development. Moreover, a single medication is expected to enhance patient compliance due to a less complicated treatment regimen, as well as a diminished number of adverse reactions and toxicity in comparison to a combination of drugs. As a consequence, many efforts have been made to design hybrid molecules of different chemical structures and functions as a means to circumvent drug resistance. The enormous number of studies in this field encouraged us to review the available literature and present selected research results highlighting the possible role of hybrid drugs in overcoming cancer drug resistance.     

Specificity in the Cu interactions with prion protein fragments and related His-rich peptides from mammals to fishes

The prion proteins may play a critical role in copper homeostasis and the antioxidant activity in the brain. This review presents the state of art in the studies on Cu²⁺ prion systems. The proteins discussed are from different species from mammals to fishes. All proteins are His-rich and the research discussed clearly indicates the basic role of imidazole side chains and the adjacent amide nitrogen atoms in metal ion binding. Prions represent the family of proteins with new mode of Cu²⁺ binding which includes the amide nitrogen coordination. The multi-imidazole coordination is also likely and it can play a critical role in the antioxidant activity of the copper–prion complexes. The combination of the imidazole and amide nitrogen atoms to Cu²⁺ ions could also be relevant in histidine-rich peptide antibiotics including demegen. The impact of peptide sequence and His positions on copper binding ability is also discussed.