Fast and selective determination of triterpenic compounds in olive leaves by liquid chromatography-tandem mass spectrometry with multiple reaction monitoring after microwave-assisted extraction

A method for fast and selective determination of the main triterpenic compounds present in olive leaves — oleanolic, ursolic and maslinic acids as triterpenic acids and, uvaol and erythrodiol as triterpenic dialcohols — is reported here. Quantitative isolation of the analytes has been accomplished in 5 min by microwave assistance using ethanol as extractant. Due to the medium polarity of triterpenic acids and dialcohols, different ethanol-water ratios were tested in order to select the optimum extractant composition for their solubilisation. Microwave assistance provided a significant shortening of the leaching time as compared to conventional procedures by maceration, which usually requires at least 5 h. After extraction, determination was carried out by liquid chromatography-tandem mass spectrometry (LC-MS-MS) with a triple quadrupole (qQq) mass detector without any clean-up step prior to chromatographic analysis. Highly selective identification of triterpenes was confirmed by multiple reaction monitoring (MRM) using the most representative transitions from the precursor ion to the different product ions, while the most sensitive transitions were used for MS-MS quantitation. Total analysis performed in 25 min enables the characterization of a fraction with particular interest in the pharmacological area.     

Anharmonic effects on lattice resonant modes of impure metallic crystals

The effect of lattice anharmonicity on the resonant modes of dilute impurities for Au-Cu, Au-Ag and W-Cr metallic systems are studied from the poles of the double time temperature dependent impure Green’s function of these crystals. The third order force constants used in the present work are derived assuming the systems to obey the Lennard-Jones potential. The inclusion of lattice anharmonicity has been found to increase the resonant frequency which depends upon the mass defect, force constant change parameter and the impurity concentration terms. Some interesting features about the phase shift and the change in width of the vibrational spectrum are reported at room temperature for the isotopic defects and the defects interacting with host atoms. The results are found to be in qualitative agreement with the experiments on the systems considered.     

Thermo‐oxidative degradation of HDPE as a function of its crystalline content

The composition, the thermal properties, and the kinetics of the thermo‐oxidative degradation of high‐density polyethylene (HDPE) were studied as a function of the increasing crystalline fraction, which resulted from the selective extraction of the amorphous part, through digestion by immersion in fuming nitric acid (HNO₃) for different periods of time. The chemical and thermodynamic changes in HDPE, brought about by digestion in nitric acid for different periods of time, are discussed. Changes in the chemistry and microstructure of the HDPE, as a function of acid treatment for different periods of time, were studied using infra‐red spectroscopy (FTIR), gel permeation chromatography (GPC), and thermal analysis (DSC and TGA), as well as scanning electron microscopy (SEM). These studies were carried out as a function of the extracted amorphous fraction of HDPE samples via digestion in HNO₃. These studies showed that in the first stages of the acid chemical attack, the amorphous part first undergoes a chemical modification and then dissolves into the strong acid medium. The total crystalline fraction apparently decreases during the first stages of the chemical attack and then increases as the amorphous part is extracted. TGA results show that as the selective extraction of the amorphous part occurs, there is a displacement of the thermo‐oxidative degradation toward higher temperatures. The kinetics of the thermo‐oxidative degradation as a function of the extraction of the amorphous part was followed according to the Horowitz‐Metzger method, and it was found that as the concentration of the crystalline fraction increases, the activation energy for the thermo‐oxidative degradation increases. SEM studies show that the extraction of the amorphous part does not affect the size of the crystalline lamellar thickness of HDPE. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1906–1915, 2009     

Homo‐ and heteropolynuclear copper(II) complexes containing a new diimine–dioxime ligand and 1,10‐phenanthroline: synthesis,characterization, solvent‐extraction studies,catalase‐like functions and DNA cleavage abilities

A series of homo‐, heterodinuclear and homotrinuclear copper(II) complexes containing a new Schiff base ligand and 1,10‐phenanthroline were synthesized. Based on results of elemental analyses, FTIR, ¹H‐ and ¹³C‐NMR spectra, conductivity measurements and magnetic susceptibility measurements, the complexes had general compositions {[Cu(L)(H₂O)M(phen)₂](ClO₄)₂ [M = Cu(II), Mn(II), Co(II)]} and {[Cu₃(L)₂(H₂O)₂](ClO₄)₂}. The metal:L:phen ratio is 2:1:2 for the dinuclear copper(II) complexes and the metal:L ratio was 3:2 for the trinuclear copper(II) complex. The liquid–liquid extraction of various transition metal cations [Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Pb(II), Cd(II), Hg(II)] from the aqueous phase to the organic phase was carried out using the diimine–dioxime ligand. It was concluded that the ligand can effectively be used in solvent extraction of copper(II) from the aqueous phase to the organic phase. Furthermore, catalytic activitiy of the complexes for the disproportionation of hydrogen peroxide was also investigated in the presence of imidazole. Dinuclear copper(II)–manganese(II) complex has some similarity to manganese catalase in structure and activity. The interaction between these complexes and DNA has also been investigated by agarose gel electrophoresis; we found that the homo‐ and heterodinuclear copper complexes can cleave supercoiled pBR322 DNA to nicked and linear forms in the presence of H₂O₂. Copyright © 2009 John Wiley & Sons, Ltd.     

Solution processed Al-doped ZnO and its performance in dye sensitized solar cells

Al-doped ZnO rods of nanometer to sub-micrometer size range have been successfully synthesized by a simple yet cost-effective solution processed sonochemical technique. Systematic XRD analysis established the solid solubility limit for Al in the ZnO lattice to be ca. 3 mol% at an elevated annealing temperature of 800 °C. The secondary ZnAl₂O₄ phase appears with increasing dopant concentrations and at lower annealing temperatures. Significant variations in the optoelectronic properties are induced by modifications in the surface defects of ZnO rods as a result of Al doping. As a consequence, an improved fill factor (FF) of 74.78 and 75.76% with a conversion efficiency (η) of 1.59 and 1.79% have been achieved for the fabricated DSSC devices made of the 800 °C annealed ZnO rods doped by 1 and 3 mol% Al, respectively.     

Refined Composite Multi-Scale Reverse Weighted Permutation Entropy and Its Applications in Ship-Radiated Noise

Ship-radiated noise is one of the important signal types under the complex ocean background, which can well reflect physical properties of ships. As one of the valid measures to characterize the complexity of ship-radiated noise, permutation entropy (PE) has the advantages of high efficiency and simple calculation. However, PE has the problems of missing amplitude information and single scale. To address the two drawbacks, refined composite multi-scale reverse weighted PE (RCMRWPE), as a novel measurement technology of describing the signal complexity, is put forward based on refined composite multi-scale processing (RCMP) and reverse weighted PE (RWPE). RCMP is an improved method of coarse-graining, which not only solves the problem of single scale, but also improves the stability of traditional coarse-graining; RWPE has been proposed more recently, and has better inter-class separability and robustness performance to noise than PE, weighted PE (WPE), and reverse PE (RPE). Additionally, a feature extraction scheme of ship-radiated noise is proposed based on RCMRWPE, furthermore, RCMRWPE is combined with discriminant analysis classifier (DAC) to form a new classification method. After that, a large number of comparative experiments of feature extraction schemes and classification methods with two artificial random signals and six ship-radiated noise are carried out, which show that the proposed feature extraction scheme has better performance in distinguishing ability and stability than the other three similar feature extraction schemes based on multi-scale PE (MPE), multi-scale WPE (MWPE), and multi-scale RPE (MRPE), and the proposed classification method also has the highest recognition rate.     

Unexpected acceleration of Ultrasonic-Assisted iodide dosimetry in the catalytic presence of ionic liquids

This study investigates the potential of using small amounts of ionic liquids (IL) to enhance ultrasound-assisted extraction of lipids content from green microalgae. Three imidazolium-based ILs (butyl, octyl and dodecyl), each of them with two anions (bromide and acetate) were tested as additives. Viscosity and surface tension of the ILs aqueous mixtures were analyzed to determine the influence of ILs’ anions and alkyl chain length, whereas KI dosimetry experiments were used as an indicator of radicals formation. A key finding suggests that the small addition of ILs improves the ultrasonication either by enhancing the viscosity and reducing the water surface tension, leading to a more powerful acoustic cavitation process or by increasing HO° production likely to oxidize the microalgae cells membranes, and consequently disrupting them on a more efficient manner. KI dosimetry also revealed that long ILs alkyl chain is detrimental. This experimental observation is confirmed thus strengthened as the yield of extracted lipids from green microalgae has shown an incremental trend when the IL concentration also increased. These hypotheses are currently under investigation to spot detailed impact of ILs on cavitation process.     

Process intensification and kinetic studies of ultrasound-assisted extraction of flavonoids from peanut shells

In this work, extraction of flavonoids from peanut shells has been studied in the presence of ultrasound and the results are compared with Soxhlet and heat reflux extraction for establishing the process intensification benefits. The process optimization for understanding the effects of operating parameters, such as ethanol concentration, particle size, solvent to solid ratio, extraction temperature, ultrasonic power and ultrasonic frequency, on the extraction of flavonoids has been investigated in details. The highest extraction yield (9.263 mg/g) of flavonoids was achieved in 80 min at optimum operating parameters of particle size of 0.285 mm, solvent to solid ratio of 40 ml/g, extraction temperature of 55 °C, ultrasonic power of 120 W and ultrasonic frequency of 45 kHz with 70% ethanol as the solvent. Two kinetic models (i.e. phenomenological model and Peleg’s model) have been introduced to describe the extraction kinetic of flavonoids by fitting experimental data and predict kinetic parameters. Good performance with slight loss of goodness of fit of two models was found by comparing their coefficient of determination (R²), root mean square error (RMSE) and/or mean percentage error (MPE) values. This work would provide the reduction of degradation and the economic evaluation for the extraction processes of flavonoids from peanut shells, as well as give a better explanation for the mechanism of ultrasound.     

Comparison of ultrasound and microwave assisted extraction of diosgenin from Trigonella foenum graceum seed

From the recent market trend, there is a huge demand for the bioactive compounds from various food matrices that could be capable enough to combat the emerging health effects in day-to-day life. Fenugreek is a well-known spice from ancient times for its medicinal and health benefits. In the present study, two methods of green extraction microwave (MAE) and ultrasound (UAE) assisted were studied in regard of extraction of fenugreek diosgenin. In this study, solvent type (acetone, ethanol, hexane and petroleum ether), solvent concentration (40, 60, 80 and 100%) and treatment time (1.5, 3.0, 4.5 and 6.0 min and 30, 40, 50 and 60 min for MAE and UAE method respectively) was varied to observe the effect of these parameters over extract yield and diosgenin content. The results of this study revealed that treatment time, type of solvent and its concentration and method adopted for extraction of diosgenin has significant effect. In relation with better yield extract and diosgenin content, the yield of fenugreek seed extract was 7.83% with MAE and 21.48% with UAE of fenugreek seed powder at 80% ethanol concentration at 6 and 60 min respectively. The content of diosgenin was observed in fenugreek seed powder extract was 35.50 mg/100 g in MAE and 40.37 mg/100 g in UAE with 80% ethanol concentration at 6 and 60 min respectively. The overall range of yield of fenugreek extract was varied from 1.04% to 32.48% and diosgenin content was 15.82 mg/100 g to 40.37 mg/100 g of fenugreek seed powder including both extraction methods. This study revealed that UAE would impose better ways for preparing fenugreek extract and observing diosgenin content from fenugreek seeds.     

Influence of ultrasound-assisted tumbling on NaCl transport and the quality of pork

The present study aimed to investigate the impact of ultrasound-assisted tumbling (UAT; 20 kHz, 100, 300, 500 and 700 W) with different treatment time (30, 60, 90 and 120 min) on the diffusion and distribution of NaCl as well as the change of pork texture properties during curing. Results showed that in comparison with the single tumbling (ST), the NaCl content and the NaCl diffusion coefficient were increased along with UAT treatment (P < 0.05). The scanning electron microscopy and the energy dispersive X-ray analysis showed that UAT treatment changed the microstructure of pork which may facilitate the NaCl dispersion homogeneously. In addition, the moderate UAT treatment of 300 W with 60 min could significantly improve the tumbling yield, water-holding capacity and textural properties of pork compared with the ST treatment (P < 0.05). Meanwhile, in comparison with the ST group, protein extraction was considerably increased after UAT (300 and 500 W) treated for 120 min (P < 0.05). Our study demonstrated that UAT treatment could effectively promote the penetration and distribution of NaCl and improve pork meat quality via facilitating the extraction of meat protein.