Rapid Determination of Simple Polyphenols in Grapes by LC Using a Monolithic Column

The development of a rapid, reliable and reproducible LC method for the determination and quantification of 13 polyphenols (gallic acid, protocatechuic aldehyde, gentisic acid, catechin, vanillinic acid, caffeic acid, vanillin, epicatechin, syringaldehyde, p-coumaric acid, ferulic acid, sinapic acid and resveratrol) in grapes and derived products is reported. The polyphenols were separated in less than 8 min. Employed was an RP-18e (100 mm × 4.6 mm) monolithic type column. A gradient method with the following solvents was utilised for the chromatographic separation: A: 90% water, 2% acetic acid in methanol, and B: 90% methanol, 2% acetic acid in water. Two detectors in series were employed: a UV–Vis detector and a fluorescence excitation/emission detector. Influence of temperature (15–40 °C) and solvent flow rate (2–5 mL min^?1) on the separation were studied, and 25 °C and 2.5 mL min^?1 were found to be the optimum conditions. The relative standard deviations of the resulting peak areas, for both intra- and inter- experiments, were less than 2.4 and 2.6%, respectively. Finally, the developed method has been utilised for the quantification of the polyphenols in real samples.     

Evaluation of an alternative convenient irradiation system for determination of emission rate of radio-isotopic neutron sources

In present work, an alternative irradiation system based on a symmetric cylindrical tank filled with a moderator containing hydrogen, which was equipped with a NaI(Tl) scintillation detector, was proposed for using in determination of neutron flux. This irradiation system was designed by MCNP4C code, with considering a ²⁴¹Am–Be neutron source in several volumes and different materials. When the neutron is captured by hydrogen, a 2.22 MeV prompt gamma-ray is emitted. The gamma pulse-height spectrum shows a photo-peak around 2.22 MeV whose net area is proportional to the total emission rate of neutron. The simulation result showed that a cylindrical tank with 110 cm diameter and height filled with water can be a suitable system for neutron source strength calibration. Furthermore, a proper two-layer shielding must be placed between the source and detector for preventing neutrons and gamma rays to directly enter the detector.     

Influence of annealing temperature on the electrochemical and surface properties of the 5-V spinel cathode material LiCr0.2Ni0.4Mn1.4O4 synthesized by a sol–gel technique

LiCr_0.2Ni_0.4Mn_1.4O₄ was synthesized by a sol–gel technique in which tartaric acid was used as oxide precursor. The synthesized powder was annealed at five different temperatures from 600 to 1,000 °C and tested as a 5-V cathode material in Li-ion batteries. The study shows that annealing at higher temperatures resulted in improved electrochemical performance, increased particle size, and a differentiated surface composition. Spinel powders synthesized at 900 °C had initial discharge capacities close to 130 mAh g^?1 at C and C/2 discharge rates. Powders synthesized at 1,000 °C showed capacity retention values higher than 85 % at C/2, C, and 2C rates at 25 °C after 50 cycles. Annealing at 600–800 °C resulted in formation of spinel particles smaller than 200 nm, while almost micron-sized particles were obtained at 900–1,000 °C. Chromium deficiency was detected at the surface of the active materials annealed at low temperatures. The XPS results indicate presence of Cr⁶⁺ impurity when the annealing temperature was not high enough. The study revealed that increased annealing temperature is beneficial for both improved electrochemical performance of LiCr_0.2Ni_0.4Mn_1.4O₄ and for avoiding formation of Cr⁶⁺ impurity on its surface.     

Thin layer spectroelectrochemical (RVC-OTTLE) studies of pertechnetate reduction in acidic media

A Peltier-cooled silicon drift detector was successfully applied for conversion electron spectrometry. The energy resolution of the detector for 45 keV electrons was 0.50 keV (FWHM). The approximate thickness of the dead layer was determined to be 140 ± 20 nm Si equivalent. The relative efficiency of the detector was verified to be approximately constant in the energy range of 17–75 keV. This is concordant with the high transparency of the thin dead layer and the sufficient thickness of the detector (450 μm) to stop the electrons. The detector is suitable for use in plutonium analysis of chemically prepared samples. Moreover, it was demonstrated that conversion electron spectrometry is better than alpha spectrometry in preserving its capability to determine the ²⁴⁰Pu/²³⁹Pu isotopic ratio as a function of sample thickness. The investigated measurement technique can be considered a promising new tool in safeguards, complementary to existing methods.     

A Sensitive and Selective RP-LC Method for the Simultaneous Determination of the Antihypertensive Drugs, Enalapril, Lercanidipine, Nitrendipine and Their Validation

A RP-LC method is presented, which is sensitive and selective for the simultaneous determination of enalapril–lercanidipine and enalapril–nitrendipine binary mixtures in their pharmaceutical dosage forms. The analyte peaks were detected using the LC method with the mobile phase ratio of methanol: water (70:30 v/v, pH 3.0) and a 1.0 mL min^?1 flow rate. The detection wavelength was selected at 210 nm using photo diode array detector and column temperature was optimized to 30 °C. Linearity was obtained at different concentration ranges for all working pharmaceutically active compounds between 0.5 and 25 μg mL^?1. The proposed methods were extensively validated according to USP 27 requirements and ICH guidelines. The methods were applied to the analysis of pharmaceutical dosage forms containing binary mixtures of enalapril–lercanidipine and enalapril–nitrendipine. Moreover, the proposed methods were applied for the degradation studies of the selected compounds. Degradation studies were conducted using stress conditions such as UV light, acidic and alkaline hydrolysis, oxidation and heat in oven, to evaluate the ability of the separation of the response of standard compounds from their degradation products.     

A Sensitive and Selective RP-LC Method for the Simultaneous Determination of the Antihypertensive Drugs,Enalapril, Lercanidipine,Nitrendipine and Their Validation

A RP-LC method is presented, which is sensitive and selective for the simultaneous determination of enalapril–lercanidipine and enalapril–nitrendipine binary mixtures in their pharmaceutical dosage forms. The analyte peaks were detected using the LC method with the mobile phase ratio of methanol: water (70:30 v/v, pH 3.0) and a 1.0 mL min⁻¹ flow rate. The detection wavelength was selected at 210 nm using photo diode array detector and column temperature was optimized to 30 °C. Linearity was obtained at different concentration ranges for all working pharmaceutically active compounds between 0.5 and 25 μg mL⁻¹. The proposed methods were extensively validated according to USP 27 requirements and ICH guidelines. The methods were applied to the analysis of pharmaceutical dosage forms containing binary mixtures of enalapril–lercanidipine and enalapril–nitrendipine. Moreover, the proposed methods were applied for the degradation studies of the selected compounds. Degradation studies were conducted using stress conditions such as UV light, acidic and alkaline hydrolysis, oxidation and heat in oven, to evaluate the ability of the separation of the response of standard compounds from their degradation products.

     

Water sorption heats on silica-alumina-based composites for interseasonal heat storage

CaCl₂-containing composites have been prepared by depositing the hydrated salt (by incipient wetness impregnation) on three different silica-aluminas with various Si/Al ratios. The surface area and porosity of all the samples were determined by N₂-adsorption at ?196 °C, and their water sorption properties were investigated by thermogravimetry linked to differential scanning calorimetry (TG–DSC) in order to determine the quantity of adsorbed/desorbed water and the related heats. The heat released and the quantity of adsorbed water were found to depend on parameters such as the silica-alumina pore diameters, the Si/Al ratio, and the presence of accessible CaCl₂ active phase. The short-term stability of both supports and composites has been also checked by performing successive hydration–dehydration cycles. The sample with the lower Si/Al ratio provided the highest heat per surface area of material, and the heat released per mol of water increased with the amount of Al₂O₃ present in the samples. The deposition of CaCl₂ positively acted on the quantity of heat released during the water sorption, and the composite with the higher alumina content (75 mass% Al) showed the largest heat released per m² of material (2.4 J m^?2) compared to those containing 25 and 13 mass% Al (1.4 and 1.2 J m^?2, respectively).     

Thermodynamic study of complex formation between dibenzo-18-crown-6 and UO2 2+ cation in different non-aqueous binary solutions

In the present work the complexation process between UO₂ ²⁺ cation and the macrocyclic ligand, dibenzo-18-crown-6 (DB18C6) was studied in ethylacetate–dimethylformamide (EtOAc/DMF), ethylacetate–acetonitrile (EtOAc/AN), and ethylacetate–tetrahydrofuran (EtOAc/THF) and ethylacetate–propylencarbonate (EtOAc/PC) binary solutions at different temperatures using the conductometric method. The results show that the stoichiometry of the (DB18C6 . UO₂)²⁺ complex in all binary mixed solvents is 1:1. A non-linear behavior was observed for changes of log K_f of this complex versus the composition of the binary mixed solvents. The stability constant of (DB18C6 . UO₂)²⁺ complex in various neat solvents at 25 °C decreases in order: THF > EtOAc > PC > AN > DMF, and in the binary solvents at 25 °C is: THF–EtOAc > PC–EtOAc > DMF–EtOAc ≈ AN–EtOAc. The values of thermodynamic quantities (?H°_c, ?S°_c) for formation of this complex in the different binary solutions were obtained from temperature dependence of its stability constant and the results show that the thermodynamics of complexation reaction between UO₂ ²⁺ cation and DB18C6 is affected strongly by the nature and composition of the mixed solvents.     

Rapid Determination of DDT and Its Metabolites in Environmental Water Samples with Mixed Ionic Liquids Dispersive Liquid–Liquid Microextraction Prior to HPLC-UV

In this paper, a novel mixed ionic liquids-dispersive liquid–liquid microextraction method was developed for rapid enrichment and determination of environmental pollutants in water samples. In this method, two kinds of ionic liquids, hydrophobic ionic liquid and hydrophilic ionic liquid, were used as extraction solvent and disperser solvent, respectively. DDT and its metabolites were used as model analytes and high-performance liquid chromatography with ultraviolet detector for the analysis. Factors that may affect the extraction recoveries, such as type and volume of extraction solvent (hydrophobic ionic liquid) and disperser solvent (hydrophilic ionic liquid), extraction time, sample pH and ionic strength, were investigated and optimized. Under the optimum conditions, the linear range was 1–100 μg L⁻¹, limits of detection could reach 0.21–0.49 μg L⁻¹, and relative standard deviation was 6.01–8.48 % (n = 7) for the analytes. Satisfactory results were achieved when the method was applied to analyze the target pollutants in environmental water samples with spiked recoveries over the range of 85.7–106.8 %.

     

Study of complex formation between 18-crown-6 and diaza-18-crown-6 with uranyl cation (UO2 2+) in some binary mixed aqueous and non-aqueous solvents

The complexation reaction between UO₂ ²⁺ cation with macrocyclic ligand, 18-crown-6 (18C6), was studied in acetonitrile–methanol (AN–MeOH), nitromethane–methanol (NM–MeOH) and propylencarbonate–ethanol (PC–EtOH) binary mixed systems at 25 °C. In addition, the complexation process between UO₂ ²⁺ cation with diaza-18-crown-6 (DA18C6) was studied in acetonitrile–methanol (AN–MeOH), acetonitrile–ethanol (AN–EtOH), acetonitrile–ethylacetate (AN–EtOAc), methanol–water (MeOH–H₂O), ethanol–water (EtOH–H₂O), acetonitrile–water (AN–H₂O), dimethylformamide–methanol (DMF–MeOH), dimethylformamide–ethanol (DMF–EtOH), and dimethylformamide–ethylacetate (DMF–EtOAc) binary solutions at 25 °C using the conductometric method. The conductance data show that the stoichiometry of the complexes formed between (18C6) and (DA18C6) with UO₂ ²⁺ cation in most cases is 1:1 [M:L], but in some solvent 1:2 [M:L₂] complex is formed in solutions. The values of stability constants (log K_f) of (18C6 · UO₂ ²⁺) and (DA18C6 · UO₂ ²⁺) complexes which were obtained from conductometric data, show that the nature and also the composition of the solvent systems are important factors that are effective on the stability and even the stoichiometry of the complexes formed in solutions. In all cases, a non-linear relationship is observed for the changes of stability constants (log K_f) of the (18C6 · UO₂ ²⁺) and (DA18C6 · UO₂ ²⁺) complexes versus the composition of the binary mixed solvents. The stability order of (18C6 · UO₂ ²⁺) complex in pure studied solvents was found to be: EtOH > AN ≈ NM > PC ≈ MeOH, but in the case of (DA18C6 · UO₂ ²⁺) complex it was : H₂O > MeOH > EtOH.     

Effects of Oxygen Addition and Treating Distance on Surface Cleaning of ITO Glass by a Non-Equilibrium Nitrogen Atmospheric-Pressure Plasma Jet

Effects of oxygen addition and treating distance on cleaning organic contaminants on stationary and non-stationary (1–9 cm/s) ITO glass surfaces by a parallel-plate nitrogen-based dielectric barrier discharge (DBD) are investigated experimentally; the DBD is driven by a 60 kHz bipolar quasi-pulsed power source. The results show that two regimes of favorable operating condition for improving the hydrophilic property of the surface (reducing the contact angle from 84° to 25–30°) are found. The measured spatial distribution of NO-γ UV emission, O₃ concentration and OES spectra are shown to strongly correlate with the measured hydrophilic property. At the near jet downstream locations (z < 10 mm), the metastable \( N_{2} (A^{3} \sum {_{u}^{ + } )} \) and photo-induced dissociation of ozone play dominant roles in cleaning the ITO glass surface; while at the far jet downstream locations (z > 10 mm), where the ratio of oxygen to nitrogen is lower, only the long-lived metastable \( N_{2} (A^{3} \sum {_{u}^{ + } )} \) plays a major role in cleaning the ITO glass surface.     

Controllable Synthesis of Covellite Nanoparticles via Thermal Decomposition Method

In this study, covellite (CuS) nanoparticles were synthesized through a facile and low temperature thermal decomposition method using [Cu(sal)₂]- oleylamine complex, (sal = salicylaldehydeato, prepared in situ from [Cu(sal)₂] and oleylamine as the precursors), and sulfur as the Cu²⁺ source and S source, respectively. Scanning electron microscope, transmission electron microscope, electron diffraction and ultraviolet–visible absorption (UV–Vis) spectra were used for the characterization of the products. The effect of reaction parameters, such as the copper:sulfur molar ratio, the reaction temperature and the reaction time on the shape, size and phase of CuS nanostructures, was investigated. The results showed that the, covellite (hexagonal structure of CuS) with an average size between 20 and 45 nm could be obtained with the Cu:S molar ratio of 1: 3 at 105 °C for 60 min. With increasing the reaction temperature from 105 to 200 °C, non-stoichiometric Cu_1.65S with the average size of 25–50 nm was obtained due to the different existing state of the released Cu²⁺ ions from the copper-oleylamine complex.     

Low temperature nanostructured lithium titanates: controlling the phase composition, crystal structure and surface area

Low temperature lithium titanate compounds (i.e., Li₄Ti₅O₁₂ and Li₂TiO₃) with nanocrystalline and mesoporous structure were prepared by a straightforward aqueous particulate sol–gel route. The effect of Li:Ti molar ratio was studied on crystallisation behaviour of lithium titanates. X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) revealed that the powders were crystallised at the low temperature of 500 °C and the short annealing time of 1 h. Moreover, it was found that Li:Ti molar ratio and annealing temperature influence the preferable orientation growth of the lithium titanate compounds. Transmission electron microscope (TEM) images showed that the average crystallite size of the powders annealed at 400 °C was in the range 2–4 nm and a gradual increase occurred up to 10 nm by heat treatment at 800 °C. Field emission scanning electron microscope (FE-SEM) analysis revealed that the deposited thin films had mesoporous and nanocrystalline structure with the average grain size of 21–28 nm at 600 °C and 49–62 nm at 800 °C depending upon the Li:Ti molar ratio. Moreover, atomic force microscope (AFM) images confirmed that the lithium titanate films had columnar like morphology at 600 °C, whereas they showed hill-valley like morphology at 800 °C. Based on Brunauer–Emmett–Taylor (BET) analysis, the synthesized powders showed mesoporous structure containing pores with needle and plate shapes. The surface area of the powders was enhanced by increasing Li:Ti molar ratio and reached as high as 77 m²/g for the ratio of Li:Ti = 75:25 at 500 °C. This is one of the smallest crystallite size and the highest surface areas reported in the literature, and the materials could be used in many applications such as rechargeable lithium batteries and tritium breeding materials.     

The preparation of a certified reference material of polar pesticides in freeze-dried water (CRM 606)

The preparation of a certified reference material of polar pesticides in freeze-dried water is described. The pesticides selected were atrazine, simazine, carbaryl, propanil, linuron, fenamiphos and permethrin which were added to 6000 litres of tap water at 50–80 μg · L^–1 (200–320 μg · L^–1 for permethrin) level in presence of NaCl (2.5 g · L^–1) prior lyophilization. After the freeze-drying process the residue was rehomogenized, filled into amber glass bottles and stored at –20?°C, +4?°C and +20?°C. All pesticides were determined by HPLC/diode array detector, except permethrin which was determined by GC/ECD. The results obtained for atrazine, simazine, carbaryl, propanil, linuron and fenamiphos showed no within- or between-bottle inhomogeneity, however the material was non-homogeneous for permethrin and therefore this was withdrawn from further studies. With respect to the stability for over one year, all pesticides were stable at –20?°C. At +4?°C all pesticides were stable for at least 9 months and at +20?°C the stability was demonstrated only during the first month of storage. The content (mass fractions) of atrazine, simazine, carbaryl, propanil and linuron in freeze-dried water (CRM 606) was certified by an interlaboratory testing and a certification campaign.     

Simultaneous Identification and Quantification of Dextran 20 and Sucrose in Lyophilized Thrombin Powder by Size Exclusion Chromatography with ELSD

A rapid and accurate size exclusion chromatography method for the simultaneous identification and quantification of dextran 20 and sucrose with optical activity in the lyophilized thrombin powder was developed and validated. The assay was conducted on a Hitachi model D-2000 Elite HPLC system with a TOSOH TSKgel G3000 PWxl column (30 cm × 7.8 mm, 7 μm particle size) and an Alltech 3300 evaporative light scattering detector (ELSD). The mobile phase was acetonitrile–water (46:54, v/v) mixture delivered at a flow rate of 0.7 mL min⁻¹ at 25 °C. The ELSD was operated at a nebulizer-gas flow rate of 2.0 L min⁻¹ and drift tube temperature of 90 °C, and the gain was set at one. Afterward, method validation system for the size exclusion chromatography analysis was developed. The linear range was 0.1–1.6 and 0.1–1.0 g L⁻¹ for dextran 20 and sucrose, respectively, and the detection limits were <0.02 g L⁻¹ for dextran 20 and <0.015 g L⁻¹ for sucrose. Inter-day and intra-day variabilities showed that RSD ranged from 0.27 to 4.20%. Recovery validation showed that average recovery was between 96.00 and 103.98%. The developed analytical procedure was successfully applied to determine the contents of dextran 20 and sucrose in the lyophilized thrombin powder.

     

Thermal analysis of contemporary glass-ionomer restorative materials

The thermal characteristics of four conventional glass-ionomer cement (GIC) dental restorative products as well as five resin-modified glass-ionomer (RMGI) materials over 1-year of storage were investigated. All materials were prepared following manufacturer’s recommendations and placed into 40 μL aluminum differential scanning calorimeter (DSC) crucibles. Samples (n = 5) were stored at 37 °C and 98 ± 2 % humidity until their appointed time of evaluation at which they were first subjected to specific heat analysis using DSC over 20–60 °C that was immediately followed by a 37–600 °C thermal scan at 10 °C min^?1. Samples were evaluated immediately after preparation, at 24 h, 1 week, 1 month, as well as at 3, 6, 9, and 12 months. Mean thermal results were compared with analysis of variance and Scheffe post-hoc testing (p = 0.05). All materials absorbed water during storage. Conventional GIC materials demonstrated increased polyalkenoate polymer maturity over the 12-month storage. The paste–paste RMGI materials, absorbed more water during storage and had increased specific heat values compared to powder–liquid RMGI materials. Of the RMGI materials investigated, only two materials demonstrated evidence of a continuing polyalkenoate matrix maturity that was within the limitations of the technology used, indicating the resin component in some newer formulations of RMGI restorative materials may severely limit the polyalkenoate reaction.     

A Sensitive Method for Methyl tert-Butyl Ether Analysis in Water Samples by a New HS-SPME Vial and GC

In this study, a new sample vial has been designed for the extraction and determination of methyl tert-butyl ether (MTBE) in water samples by headspace solid-phase microextraction method. The special feature of this new vial is cooling the HS above the aqueous sample by cold water stream for maximum analyte absorption on SPME fiber coating. The analysis was by a gas chromatograph equipped with flame ionization detector and a capillary column (CP-sil 13 CB). Some significant variables affecting the extraction procedure were optimized. By use of divinylbenzene/carboxen/polydimethylsiloxane fiber, a sample volume of 10 mL, stirring rate of 1,000 rpm, salt concentration of 24%, extraction time of 15 min and extraction temperature of 83 °C, detection limit of 0.022 μg L⁻¹ and a good linearity (R ² = 0.998) in a calibration range of 0.1–400 μg L⁻¹ were achieved. The relative standard deviation for triplicate runs ranged between 6 and 8%. The method could be applied to the analysis of trace levels of MTBE in various water samples.

     

Spectrometric and Chromatographic Study of Reactive Oxidants Hypochlorous and Hypobromous Acids and Their Interactions with Taurine

In this study, we focused on the studying of taurine complexes with phenol and sodium hypochlorite, and of taurine with sodium hypobromite by spectrometry, reverse phase chromatography and ion-exchange chromatography. The formed complexes were studied under various conditions such as temperature (10, 20, 30, 40, 50 and 60 °C), and/or time of interaction (0, 5, 10, 15, 20, 25 and 30 min). In addition, we optimized high performance liquid chromatography coupled with UV detector for detection of taurine and its complexes with the acids. Taurine–phenol–hypochlorite complex was effectively separated under isocratic elution, mobile phase water:methanol 30:70 %, v:v, flow rate 1 mL min^?1 and 55 °C. Taurine-bromamine complex was isolated under the following optimized conditions as isocratic elution, mobile phase water:methanol 85:15 % v:v, flow rate 1 mL min^?1 and 55 °C. The limits of detection (3 S/N) were estimated as 1 μM for both types of complexes, i.e. for taurine. Further, we estimated recovery in one sample of urine (male 25 years), commercially achieved energy drink and tea leaves and varied from 79 to 86 %. Further, we aimed our attention at investigating the ability of the above characterized taurine and taurine complexes to scavenge reactive oxygen species. For this purpose, an ion-exchange liquid chromatography with post-column derivatization with ninhydrin and VIS detector was used. It clearly follows from the results obtained that taurine itself reacts with peroxide more intensely than in a bound form, which can be associated with the highest signal decrease. Complexes stabilized structure taurine against peroxide radicals, resulting in slower decreasing of peak heights. The most stable was taurine complexes with phenol and hypobromite.     

Hydrotalcite-derived Co-containing mixed metal oxide catalysts for methanol incineration

The Co–Mg–Al mixed metal oxides were prepared by calcination of co-precipitated hydrotalcite-like precursors at various temperatures (600–800 °C), characterised with respect to chemical (AAS) and phase (XRD) composition, textural parameters (BET), form and aggregation of cobalt species (UV–vis-DRS) and their redox properties (H₂-TPR, cyclic voltammetry). Moreover, the process of thermal decomposition of hydrotalcite-like materials to mixed metal oxide systems was studied by thermogravimetric method combined with the analysis of gaseous decomposition products by mass spectrometry. Calcined hydrotalcite-like materials were tested as catalysts for methanol incineration. Catalytic performance of the oxides depended on cobalt content, Mg/Al ratio and calcination temperature. The catalysts with lower cobalt content, higher Mg/Al ratio and calcined at lower temperatures (600 or 700 °C) were less effective in the process of methanol incineration. In a series of the studied catalysts, the best results, with respect to high catalytic activity and selectivity to CO₂, were obtained for the mixed oxide with Co:Mg:Al molar ratio of 10:57:33 calcined at 800 °C. High activity of this catalyst was likely connected with the presence of a Co–Mg–Al spinel-type phases, containing easy reducible Co³⁺ cations, formed during high-temperature treatment of the hydrotalcite-like precursor.