Synthesis,spectral investigation and development of tetrahedral copper(II) complexes as artificial metallonucleases and antimalarial agents

Seven new copper(II) complexes of type [Cu(A)(L)]?H₂O (A = sparfloxacin, ciprofloxacin, levofloxacin, gatifloxacin, pefloxacin, ofloxacin, norfloxacin; L = 5‐[(3‐chlorophenyl)diazenyl]‐4‐hydroxy‐1,3‐thiazole‐2(3H)‐thione) were synthesized and characterized using elemental and thermogravimetric analyses, and electronic, electron paramagnetic resonance (EPR), Fourier transform infrared and liquid chromatography–mass spectroscopies. Tetrahedral geometry around copper is assigned in all complexes using EPR and electronic spectral analyses. All complexes were investigated for their interaction with herring sperm DNA utilizing absorption titration (K_b = 1.27–3.13 × 10⁵ M^?1) and hydrodynamic volume measurement studies. The studies suggest the classical intercalative mode of DNA binding. The cleavage reaction on pUC19 DNA was monitored by agarose gel electrophoresis. The results indicate that the Cu(II) complexes can more effectively promote the cleavage of plasmid DNA. The superoxide dismutase mimic activity of the complexes was evaluated by nitroblue tetrazolium assay, and the complexes catalysed the dismutation of superoxide at pH = 7.8 with IC₅₀ values in the range 0.597–0.900 μM. The complexes were screened for their in vitro antibacterial activity against five pathogenic bacteria. All the complexes are good cytotoxic agents and show LC₅₀ values ranging from 5.559 to 11.912 µg ml^?1. All newly synthesized Cu(II) complexes were also evaluated for their in vitro antimalarial activity against Plasmodium falciparum strain (IC₅₀ = 0.62–2.0 µg ml^?1). Copyright © 2015 John Wiley & Sons, Ltd.     

Sensitive targeted multiple protein quantification based on elemental detection of Quantum Dots

A generic strategy based on the use of CdSe/ZnS Quantum Dots (QDs) as elemental labels for protein quantification, using immunoassays with elemental mass spectrometry (ICP-MS), detection is presented. In this strategy, streptavidin modified QDs (QDs-SA) are bioconjugated to a biotinylated secondary antibody (b-Ab₂). After a multi-technique characterization of the synthesized generic platform (QDs-SA-b-Ab₂) it was applied to the sequential quantification of five proteins (transferrin, complement C3, apolipoprotein A1, transthyretin and apolipoprotein A4) at different concentration levels in human serum samples. It is shown how this generic strategy does only require the appropriate unlabeled primary antibody for each protein to be detected. Therefore, it introduces a way out to the need for the cumbersome and specific bioconjugation of the QDs to the corresponding specific recognition antibody for every target analyte (protein). Results obtained were validated with those obtained using UV–vis spectrophotometry and commercial ELISA Kits.     

Crystallization of Poly(ethylene adipate) within γ-Phase Poly(vinylidene fluoride) Matrix

The effects of PEA on the γ-phase PVDF crystal structure and the crystallization of PEA within the pre-existing γ-phase PVDF spherulites have been investigated by optical microscopy(OM), infrared spectroscopy(IR) and scanning electron microscopy(SEM). The results demonstrate that the γ-phase PVDF spherulites consist of the lamellae exhibiting a highly curved scroll-like morphology and develop preferentially in PEA-rich blend. With increasing PEA concentration, the scroll diameter increases and the scrolls are better separated from each other. PEA crystallizes first in the interspherulitic region and transcrystalline layer develops. Subsequently, the transcrystalline layer of PEA continues to grow within the γ-phase PVDF spherulites, e.g., in the region between the scrolls, until impinging on other PEA transcrystalline layers or spherulites. The crystallization kinetics results indicate that the growth rate of PEA crystals in the intraspherulitic region of γ-phase PVDF shows a positive correlation with content of PEA, but a negative one with the crystallization temperature of γ-phase PVDF.     

TDPAC and first-principles study of electronic and structural properties of a Pd-vacancy complex in undoped germanium

Pd is one of the metals suitable for inducing low-temperature crystallization in Ge. However, it is not clear how residual Pd atoms are integrated into the Ge lattice. Therefore, time-differential γ–γ perturbed angular correlations (TDPAC) technique using the ¹⁰⁰Pd(→¹⁰⁰Rh) nuclear probe produced by recoil implantation has been applied to study the hyperfine interactions of this probe in single-crystalline undoped Ge. A Pd-vacancy complex aligned along the <111> crystallographic direction with a unique interaction frequency of 8.4(5) Mrad/s has been identified. This complex was measured to have a maximum relative fraction of about 76(4)% following annealing at 350 ^°C. Further annealing at higher temperatures reduced this fraction, possibly via dissociation of the complex. Calculations suggest dissociation energy of 1.94(5) eV for the complex. DFT calculations performed in this work are in reasonable good agreement with the experimental values for the electric-field gradient of the defect complex in Ge and Si for comparison. The calculations predict a split-vacancy configuration with the Pd on a bond-centred interstitial site having a nearest-neighbour semi-vacancy on both sides (V-Pd_BI-V) in Ge and Si.     

A sensitive and efficient method for trace analysis of some phenolic compounds using simultaneous derivatization and air‐assisted liquid–liquid microextraction from human urine and plasma samples followed by gas chromatography–nitrogen phosphorous detection

In present study, a simultaneous derivatization and air‐assisted liquid–liquid microextraction method combined with gas chromatography–nitrogen phosphorous detection has been developed for the determination of some phenolic compounds in biological samples. The analytes are derivatized and extracted simultaneously by a fast reaction with 1‐flouro‐2,4‐dinitrobenzene under mild conditions. Under optimal conditions low limits of detection in the range of 0.05–0.34 ng mL^?1 are achievable. The obtained extraction recoveries are between 84 and 97% and the relative standard deviations are less than 7.2% for intraday (n = 6) and interday (n = 4) precisions. The proposed method was demonstrated to be a simple and efficient method for the analysis of phenols in biological samples. Copyright © 2015 John Wiley & Sons, Ltd.     

Identification of metabolites of rupestonic acid in rat urine by liquid chromatography combined with electrospray ionization quadrupole time‐of‐flight tandem mass spectrometry

Rupestonic acid, a potential anti‐influenza agent, is an important and characteristic compound in Artemisia rupestris L., a well‐known traditional Uighur medicine for the treatment of colds. In the present study, high‐performance liquid chromatography combined with electrospray ionization quadrupole time‐of‐flight tandem mass spectrometry was used to detect and identify the metabolites in rat urine after oral administration of rupestonic acid. A total of 10 metabolites were identified or partially characterized. The structure elucidations of the metabolites were performed by comparing the changes in accurate molecular masses and fragment ions with those of the parent compound. The results showed that the main metabolites of rupestonic acid in rat urine were formed by oxidation, hydrogenation and glucuronidation. A metabolism pathway was proposed for the first time based on the characterized structures. This metabolism study can provide essential information for drug discovery, design and clinical application of rupestonic acid. Copyright © 2014 John Wiley & Sons, Ltd.     

Metabolomics techniques applied in the investigation of phenolic acids from the agro-industrial by-product of Carapa guianensis Aubl

Processing of Carapa guianensis seeds to obtain oil on an industrial scale generates a significant amount of by-product, approximately 66% w/w, which is called cake and is a potential source of biomolecules, including simple phenolic structures. For this reason, studies were carried out on the chemical profiles of hydrolyzed extract from this agro-industrial by-product through High Performance Thin-Layer Chromatography (HPTLC) and Gas Chromatography coupled to Mass Spectrometry (GC–MS). These techniques were used to detect metabolic classes and/or groups, and to identify, for the first time, thirteen simple phenolic acids in this by-product. The sample antioxidant capacity was determined by methods of 2,2-diphenyl-1-picrylhydrazyl (DPPH)and 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS⁺) radicals direct sequestration. The hydrolyzed fraction showed a total of 63.47% in the relative abundance of the total of compounds, standing out: p-hydroxybenzoic acid (39.19%) and protocatechuic acid (3,4-dihydroxybenzoic acid) (5.62%), both from hydroxybenzoic acids and 3-(3,4-dihydroxyphenyl)lactic acid, (7.76%) hydroxycinnamic acids derivatives. In these results, the fraction rich in simple phenolic acids was obtained, attributing the prominent behavior of this matrix antioxidant activity, expressed by (IC₅₀: of 16.42 µg/mL and 6.52 µg/mL for DPPH and ABTS⁺ radicals, respectively). The research demonstrated an alternative to applicability that involves sustainability from agro-industrial. These techniques were used to detect metabolic classes and/or groups, and to identify, for the first time, thirteen simple phenolic acids in this by-product, generating a process capable of converting biomass into a bioproduct, consisting of bioactive compounds, in addition to adding value to the industrial chain.