Preparation of sinapinaldehyde modified mesoporous silica materials and their application in selective extraction of trace Pb(II)

A new solid phase extractant, sinapinaldehyde (SA) modified SBA-15 mesoporous silica, was developed for selective extraction and preconcentration of trace Pb(II) from aqueous solutions. The successful immobilization of SA on SBA-15 and the strong interaction between SA-SBA-15 and Pb(II) were characterized and confirmed by FTIR spectroscopy and scanning electron microscopy. Parameters such as solution pH, shaking time, eluent condition and sample volume were optimized so that the maximum removal of Pb(II) from solution could be achieved. At pH 4.0, the maximum adsorption capacity of the sorbent for Pb(II) was found to be 33.6?mg?g^?1 and the adsorbed Pb(II) could be completely eluted using a mixed solution of 2?M HCl and 5% CS(NH₂)₂. Some common metal ions such as K(I), Na(I), Mg(II), Ca(II), Cr(III), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) did not interfere with the adsorption of trace Pb(II). The detection limit of the present method was found to be 1.3?ng?mL^?1 and the relative standard deviation was less than 2.0% (n?=?8). These results suggested that this new sorbent is very efficient and selective for the removal of trace Pb(II) in water samples.     

Solid Introduction to an ICP-Atomic Emission Spectrometer for the Analyses of Metals Contents of Air Filters

The direct introduction of solid samples (air filters) to the inductively coupled plasma source of an atomic emission spectrometer using a furnace atomizer has been studied. Conditions have been found for the analysis of elements which volatilize with varyling degrees of difficulty. Lead, copper and vandaium compounds retained on glass fibre filters from air pollution studies have been determined. The results are in good agreement with those obtained by means of established sample dissolution/atomic emision methods.     

Determination of Cadmium and Lead in Sea Water after Extraction Using Electrothermal Atomisation. Minimisation of Interferences from Co-Extracted Sea Salts

Abstract

Interferences from small amounts of sea salt in the determination of cadmium and lead were investigated. Test samples were made to mimic solutions obtained after extraction of sea water for trace metal analysis. Sea salt concentrations in the range 0–400 mg/l were investigated. Background absorption from this salt was high but easily minimised through the addition of nitric acid (2 % v/v). Sensitivity reductions due to the salt were considerable and varied from one graphite tube to the other. This problem was overcome by the addition of 1000 mg lanthanum per litre of sample. The positive effect of the lanthanum matrix modification is thought to be due to a change of the graphite tube surface.     

A Microcell for Stripping Analysis with Glassy Carbon and Mercury-Plated Glassy Carbon Electrodes

Abstract

A microcell has been constructed for stripping analysis in solution volumes as low as 5 μl, employing a glassy carbon or mercury-plated glassy carbon working electrodes and a three electrode system. Using normal d.c. stripping techniques, as little as 100 picograms of mercury and 10 picograms of lead can be determined. With the more sensitive second harmonic a.c. voltammetric technique, this limit is lowered to 10 picograms of mercury and 1 picogram of lead.     

Simultaneous Determination of Arsenic and Lead in Vegetable Oil by Atomic Fluorescence Spectrometry after Vortex-Assisted Extraction

Hydride generation atomic fluorescence spectrometry (HG-AFS) is used for the determination of hydride-forming elements due to its high sensitivity, simplicity, and low cost. A new HG-AFS method for the simultaneous determination of arsenic and lead in vegetable oil is reported. Vortex-assisted extraction with dilute nitric acid was used to isolate arsenic and lead from vegetable oil. The conditions influencing the fluorescence signal, including the carrier fluid, oxidizing agent, and reducing agent, were optimized. The interferences of coexisting ions were also evaluated. Under the optimized conditions, the limits of detection were 0.6 and 0.4?µg?kg^?1 for arsenic and lead. The recoveries were from 84.4 to 105% for both metals in vegetable oil. The optimized method was used for the determination of arsenic and lead in commercial vegetable oil. The analytical results by this approach were in good agreement with values obtained by inductively coupled plasma mass spectrometry with microwave digestion.     

An Enzyme-Linked Immunosorbent Assay for Determination of Dicyclanil in Animal Tissue

Dicyclanil is a toxic, pyrimidine-derived insect growth regulator used in veterinary medicine for the prevention of myiasis. A competitive indirect enzyme-linked immunosorbent assay was developed firstly for the determination of dicyclanil in animal tissue. The antigen was prepared using the glutaraldehyde method and polyclonal antibodies were obtained by immunizing rabbits with a dicyclanil-bovine serum albumin conjugate. The antibody obtained was specific for dicyclanil with an IC₅₀ of 9 ng/mL. Recoveries from sheep tissue and liquid milk were in the range of 52.5–72.4%, with coefficients of variation between 4.7% and 11.9%. The results were further confirmed by high performance liquid chromatography–tandem mass spectrometry.     

Biological studies and computational modeling of two new copper complexes derived from β-diketones and their nano-complexes

Abstract

The present study was conducted to design and develop new complexes and their metal-based nanodrug (registered as Casiopeínas^® for cancer) with a low toxicity, high efficiency, and high selectivity. First, complexes ([Cu(TTA)(bpy)₂] (1) and [Cu(TTA)₂(en)] (2) (TTA = 4,4,4-trifluoro-1-(2-furyl)-1,3-butanedione) were synthesized and characterized by X-ray diffraction studies, CHN analysis, conductivity measurements, FT-IR and UV-vis spectroscopy. Second, nanoparticles (NPs) of 3 and 4 with the average size of 63.04 and 85.39?nm were prepared with ultrasound. Scanning electron microscopy patterns of 3 and 4 showed irregular spherical and nanorod particles with spongy surface. Furthermore, the anticancer properties of compounds and nano-compounds were studied in MKN-45 cell line. Then, apoptosis studies were carried out utilizing AO/EB staining methods. Finally, to confirm the in vitro experimental data, the theoretical study was carried out by molecular docking studies. The results of DNA docking analysis revealed that 1 and 2 were inserted with DNA via the minor groove. The binding affinity monitors the order of 1?>?2, with a preference of binding to A-T over G-C base pairs sequences.     

Degradation effects in the extraction of antioxidants from birch bark using water at elevated temperature and pressure

Experiments with birch bark samples have been carried to enable a distinction between extraction and degradation effects during pressurised hot water extraction. Two samples, E80 and E180, contained birch bark extracts obtained after extraction at 80 and 180 °C for up to 45 min, respectively. Two other samples, P80 and P180, were only extracted for 5 min at the two temperatures and were thereafter filtered and hydrothermally treated at 80 and 180 °C, respectively. During the latter treatment, samples were collected at different times to assess the stability of the extracted compounds. An offline DPPH (2,2-diphenyl-1-picrylhydrazyl) assay, as well as a high performance liquid chromatographic separation coupled to an electrochemical detector, were used to determine the antioxidant capacity of the processed samples. The results obtained with the different techniques were compared to assess the yield of the extraction and degradation processes. In addition, an online hyphenated system comprising high performance liquid chromatography coupled to diode-array; electrochemical; and tandem mass spectrometric detection (HPLC-DAD-ECD-MS/MS) was used to study the compositions of the extracts in more detail. The results for the samples processed at 80 °C showed that the extraction reached a steady-state already after 5 min, and that the extracted compounds were stable throughout the entire extraction process. Processing at 180 °C, on the other hand, gave rise to partly degraded extracts with a multitude of peaks in both the diode array and electrochemical detectors, and a higher antioxidant capacity compared to for the extracts obtained at 80 °C. It is concluded that HPLC-DAD-ECD is a more appropriate technique for the determination of antioxidants than the DPPH assay. The mass spectrometric results indicate that one of the extracted antioxidants, catechin, was isomerised to its diastereoisomers; (+)-catechin, (−)-catechin, (+)-epicatechin, and (−)-epicatechin.     

Computer Assisted Spectrophotometric Analysis of Three Component Mixtures (Caffeine Mixtures and Codeine Mixtures)

Abstract

Two mixtures (caffeine mixture (I) and codeine mixture (II)) of 3-components, containing acetaminophen and salicylamide as majors, have been assayed using different computer-assisted spectrophotometric methods. These methods are the Unique Absorbance Method (UAM), the Unique Orthogonal Function Method (UOFM), and Unique Fourier Function Method (UFFM), and also their correspondences under the least squares approach. The parameters have been optimized for the accurate determination of the minor component caffeine in mixture (I). In mixture (II), however. codeine has been extracted - in two steps-prior to the correction of interferences from the major components acetaminophen and salicylamide.     

Solid‐State Structural Transformations and Photoreactivity of 1D‐Ladder Coordination Polymers of PbII

An attempt has been made to design double‐stranded ladder‐like coordination polymers (CPs) of hemidirected Pb^II. Four CPs, [Pb(μ‐bpe)(O₂C‐C₆H₅)₂] ? 2H₂O ( 1 ), [Pb₂(μ‐bpe)₂(μ‐O₂C‐C₆H₅)₂(O₂C‐C₆H₅)₂] ( 2 ), [Pb₂(μ‐bpe)₂(μ‐O₂C‐p‐Tol)₂(O₂C‐p‐Tol)₂] ? 1.5 H₂O ( 3 ) and [Pb₂(μ‐bpe)₂(μ‐O₂C‐m‐Tol)₂(O₂C‐m‐Tol)₂] ( 4 ) (bpe=1,2‐bis(4′‐pyridyl)ethylene), have been synthesised and investigated for their solid‐state photoreactivity. CPs 2 – 4 , having a parallel orientation of bpe molecules in their ladder structures and being bridged by carboxylates, were found to be photoreactive, whereas CP 1 is a linear one‐dimensional (1D) CP with guest water molecules aggregating to form a hydrogen‐bonded 1D structure. The linear strands of 1 were found to pair up upon eliminating lattice water molecules by heating, which led to the solid‐state structural transformation of photostable linear 1D CP 1 into photoreactive ladder CP 2 . In the construction of the double‐stranded ladder‐like structures, the parallel alignment of C?C bonds in 2 – 4 is dictated by the chelating and μ₂‐η²:η¹ bridging modes of the benzoate and toluate ligands. The role of solvents in the formation of such double‐stranded ladder‐like structures has also been investigated. A single‐crystal‐to‐single‐crystal transformation occurred when 4 was irradiated under UV light to form [Pb₂(rctt‐tpcb)(μ‐O₂C‐m‐Tol)₂(O₂C‐m‐Tol)₂] ( 5 ).