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.     

A volatolomic approach using cerumen as biofluid to diagnose bovine intoxication by Stryphnodendron rotundifolium

An innovative volatolomic approach employs the detection of biomarkers present in cerumen (earwax) to identify cattle intoxication by Stryphnodendron rotundifolium Mart., Fabaceae (popularly known as barbatimão). S. rotundifolium is a poisonous plant with the toxic compound undefined and widely distributed throughout the Brazilian territory. Cerumen samples from cattle of two local Brazilian breeds (‘Curraleiro Pé-Duro’ and ‘Pantaneiro’) were collected during an experimental intoxication protocol and analyzed using headspace (HS)/GC–MS followed by multivariate analysis (genetic algorithm for a partial least squares, cluster analysis, and classification and regression trees). A total of 106 volatile organic metabolites were identified in the cerumen samples of bovines. The intoxication by S. rotundifolium influenced the cerumen volatolomic profile of the bovines throughout the intoxication protocol. In this way, it was possible to detect biomarkers for cattle intoxication. Among the biomarkers, 2-octyldecanol and 9-tetradecen-1-ol were able to discriminate all samples between intoxicated and nonintoxicated bovines. The cattle intoxication diagnosis by S. rotundifolium was accomplished by applying the cerumen analysis using HS/GC–MS, in an easy, accurate, and noninvasive way. Thus, the proposed bioanalytical chromatography protocol is a useful tool in veterinary applications to determine this kind of intoxication.     

Fermentation characteristics and the dynamic trend of chemical components during fermentation of Massa Medicata Fermentata

As a representative of traditionally fermented Chinese medicine, Massa Medicata Fermentata (MMF) shows the functions of invigorating the spleen and stomach and promoting digestion, which plays an important role in the treatment of gastrointestinal diseases. The fermentation mechanism and the key factors that affect the quality of MMF have not been revealed yet, which has become an urgent issue that limits its clinical application. This article aims to systematically and comprehensively reveal the transformation of physical properties and the dynamic trend of chemical components including substrate components, volatile components, and lactic acid as anaerobic fermentation product during MMF fermentation. Along with obvious hyphae growth observed for MMF, the weight of MMF decreased, and the moisture and temperature increased. Through the quantified 14 components from substrate, ferulic acid increased from 45.53 ± 6.94 to 141.89 ± 78.40 μg/g, while glycosides and phenolic acids declined except caffeic acid. Also, within the 66 volatile components analyzed, alcohols and acids increased, while aldehydes and ketones decreased. Lactic acid was not detected in the fermentation substrate, but an apparent increase in lactic acid content was observed along with the increased fermentation days, resulting in 2.54 ± 0.15 mg/g on day 8. Based on the tested components, the fermentation process of MMF was discriminated into three distinct stages by principal component analysis, and an optimal fermentation time of four days was proposed. The results of this study will be of great significance to clarify the characteristics of fermentation and conduce to improving quality standards of MMF.     

SPME – A valuable tool for investigation of flower scent

A novel Headspace Solid Phase Microextraction (HS‐SPME) protocol is proposed for the analysis of floral scent. Volatile compounds emitted from the flower are collected on a Carboxen/PDMS fiber for 1 hour, transferred to the GC, and analyzed by GC/MS. The method completely eliminates the use of organic solvents, does not require special instrumentation, and may readily be performed in the field without access to mains electricity and other energy supplies. The method is robust, sensitive, and reduces the sampling stress on the investigated plant. Since enzymatic reactions in living flowers may cause changes in the composition of emitted fragrance, dried rosemary (Rosmarinus officinalis L.) was used as a stable standard for the method development and optimization. In addition, grape wine was also suggested as homogeneous, bio‐compatible, and relatively stable standard of pronounced and typical scent for the same purpose. The optimized method was used for the comparative investigation of the fragrances emitted by two different species – Lathyrus vernus (L.) and Orchis pallens (L.). Several monoterpenes (C10 compounds) were found as the main fragrance components of lathyrus, while sesquiterpenes (C15 compounds) were typical for the orchid.     

Low‐energy ion scattering: Determining overlayer thickness for functionalized gold nanoparticles

With the widespread use of engineered nanoparticles for biomedical applications, detailed surface characterization is essential for ensuring reproducibility and the quality/suitability of the surface chemistry to the task at hand. One important surface property to be quantified is the overlayer thickness of self‐assembled monolayer (SAM) functionalized nanoparticles, as this information provides insight into SAM ordering and assembly. We demonstrate the application of high sensitivity low‐energy ion scattering (HS‐LEIS) as a new analytical method for the fast thickness characterization of SAM functionalized gold nanoparticles (AuNPs). HS‐LEIS demonstrates that a complete SAM is formed on 16‐mercaptohexadecanoic acid (C16COOH) functionalized 14 nm AuNPs. HS‐LEIS also experimentally provides SAM thickness values that are in good agreement with previously reported results from simulated electron spectra for surface analysis of X‐ray photoelectron spectroscopy data. These results indicate HS‐LEIS is a valuable surface analytical method for the characterization of SAM functionalized nanomaterials. Copyright © 2013 John Wiley & Sons, Ltd.     

Storage stability studies for tributyltin determination in human urine samples using headspace solid‐phase microextraction and gas chromatography mass spectrometry

A headspace solid‐phase micro‐extraction (HS‐SPME) method was employed in order to study the effect of storage conditions of human urine samples spiked with tributyltin (TBT) using gas chromatography and mass spectrometry. To render the analyte more volatile, the derivatization (ethylation) was made in situ by sodium tetraethylborate (NaBEt₄), which was added directly to dilute unpreserved urine samples and in buffers of similar acidity. The stability of TBT in human urine matrix was compared with the stability of TBT in buffer solutions of similar pH value. Critical parameters of storage conditions such as temperature and time, which affect the stability of TBT in this kind of matrix, were examined extensively. The tests showed that the stability of TBT remains practically satisfactory for a maximum of 2 days of storage either at +4 or 20°C. Greater variations were observed in the concentration of TBT in human urine samples at +4°C and lower ones at ?20°C over a month's storage. The freeze–thaw cycles have negative effect on the stability and should be kept to a minimum. The results from spiked urine samples are also discussed in comparison to those acquired from buffer solutions of equal TBT concentration. Copyright © 2012 John Wiley & Sons, Ltd.     

The Use of Various Chromatographic Techniques for the Determination of Phenylurea Herbicides and Their Corresponding Anilines in Environmental Samples,II. Applications

Abstract

In earlier work, various strategies have been developed for the trace-level determination of phenylurea herbicides and the anilines which are their main degradation products. They include catalytic hydrolysis of the phenylureas on silica, liquid chromatographic fractionation of complex mixtures of herbicides and anilines, derivatization of anilines and herbicides with electron-capture-sensitive reagents, and final analysis by means of capillary gas chromatography. In the present paper, the application of these principles to trace-level analysis of surface water, soil and crop samples is demonstrated.     

顶空进样GC-MS结合保留指数分析墨旱莲挥发性成分

采用顶空-气相色谱-质谱法(HS-GC-MS)对墨旱莲的挥发性成分进行检测,并结合保留指数对其分析鉴定。结果检测到60个组分,鉴定出33个可能的组分,占挥发性成分的70.0%。该研究为墨旱莲药材挥发性成分的指纹图谱研究奠定了基础。     

Simple and automatic determination of aldehydes and acetone in water by headspace solid-phase microextraction and gas chromatography-mass spectrometry

We describe a simple and automatic method to determine nine aldehydes and acetone simultaneously in water. This method is based on derivatization with 2,2,2-trifluoroethylhydrazine (TFEH) and consecutive headspace-solid-phase microextraction and gas chromatography-mass spectrometry. Acetone-d(6) was used as the internal standard. Aldehydes and acetone in water reacted for 30 min at 40°C with TFEH in a headspace vial and the formed TFEH derivatives were simultaneously vaporized and adsorbed on polydimethylsiloxane-divinylbenzene. Under the established condition, the method detection limit was 0.1-0.5 μg/L in 4 mL water and the relative standard deviation was less than 13% at concentrations of 0.25 and 0.05 mg/L. This method was applied to determine aldehydes and acetone in 5 mineral water and 114 surface water samples. All mineral water samples had detectable levels of methanal (24.0-61.8 μg/L), ethanal (57.7-110.9 μg/L), propanal (11.5-11.7 μg/L), butanal, pentanal (3.3-3.4 μg/L) and nonanal (0.3-0.4 μg/L). Methanal and ethanal were also detected in concentration range of 2.7-117.2 and 1.2-11.9 μg/L, respectively, in surface water of 114 monitoring sites in Korea.