Preconcentration and determination of trace metals by flow injection micelle-mediated extraction using flame atomic absorption spectrometry

Micelle-mediated extraction/preconcentration is incorporated on-line into a flow injection system used to determine low levels of Cd(II), Co(II), Cu(II), Mn(II), Ni(II), Pb(II) and Zn(II) present in various samples. The analyte is complexed with HBDAP (N,N′-bis(2-hydroxy-5-bromo-benzyl)1,2-diaminopropane). Under optimal conditions, a solution of 30% (m/v) NaCl and a sample solution containing 2.5 mL of 1% (m/v) sodium dodecyl sulfate (SDS), 0.5 mL of 1.8 × 10⁻³ M HBDAP and 2.5 mL of pH 8.5 borate buffer solution in 25 mL were pumped through the cotton filled mini-column; onto which the surfactant-rich phase containing the complex is collected. A solution of 0.5 M HNO₃ in 50% acetone is used as the eluent. The limits of detection are (ng mL⁻¹) Cd = 0.39, Cu = 3.2, Co = 7.5, Mn = 3.0, Ni = 3.4, Pb = 17.9 and Zn = 0.89 if the sample is allowed to flow for 30 s, but improved for extended preconcentration periods. Analysis of liquid and solid reference materials showed good agreement with the certified values. Complex formation constants between HBDAP and these metal ions were also determined potentiometrically.     

Effect of oxide thickness on the capacitance and conductance characteristics of MOS structures

In this work, the investigation of the interface states density and series resistance from capacitance–voltage (C–V) and conductance–voltage (G–V) characteristics in Au/SnO₂/n-Si (MOS) structures prepared at various SnO₂ layer thicknesses by spray deposition technique have been reported. It is fabricated five samples depending on deposition time. The thicknesses of SnO₂ films obtained from the measurement of the oxide capacitance in the strong accumulation region for MOS Schottky diodes are 37, 79, 274, 401, and 446 Å, for D1, D2, D3, D4, and D5 samples, respectively. The C–V and G–V measurements of Au/SnO₂/n-Si MOS structures are performed in the voltage range from −6 to +10 V and the frequency range from 500 Hz to 10 MHz at room temperature. It is observed that peaks in the forward C–V characteristics appeared because of the series resistance. It has been seen that the value of the series resistance R_s of samples D1 (47 Ω), D2 (64 Ω), D3 (98 Ω), D4 (151 Ω), and D5 (163 Ω) increases with increasing the oxide layer thickness. The interface state density D_it ranges from 2.40×10¹³ cm⁻² eV⁻¹ for D1 sample to 2.73×10¹² cm⁻² eV⁻¹ for D5 sample and increases with increasing the oxide layer thickness.     

Santamarine Shows Anti-Photoaging Properties via Inhibition of MAPK/AP-1 and Stimulation of TGF-β/Smad Signaling in UVA-Irradiated HDFs

Chronic UVA exposure results in elevated reactive oxygen species in skin which leads to photoaging characterized as upregulated matrix metalloproteinase (MMP)-1 and loss of collagen. Therefore, natural antioxidants are hailed as promising agents to be utilized against photoaging. In the current study, reynosin and santamarine, two known sesquiterpene lactones isolated from Artemisia scoparia, were analyzed for their anti-photoaging properties in UVA-irradiated human dermal fibroblasts (HDFs). Results showed that UVA irradiation (8 J/cm²) upregulated the MMP-1 secretion and expression, and suppressed collagen production, which were significantly reverted by santamarine treatment (10 µM). Although both reynosin and santamarine exhibited ROS scavenging abilities, reynosin failed to significantly diminish UVA-stimulated MMP-1 release. UVA-irradiated HDFs showed increased collagen production when treated with santamarine. As a mechanism to suppress MMP-1, santamarine significantly suppressed the UVA-induced phosphorylation of p38 and JNK and nuclear translocation of p-c-Fos and p-c-Jun. Santamarine promoted collagen I production via relieving the UVA-induced suppression on TGF-β and its downstream activator Smad2/3 complex. Antioxidant properties of santamarine were also shown to arise from stimulating Nrf2-dependent expression of antioxidant enzymes SOD-1 and HO-1 in UVA-irradiated HDFs. In conclusion, santamarine was found to be a promising natural antioxidant with anti-photoaging properties against UVA-induced damages in HDFs.     

Synthesis and Antinociceptive Effect of Some Thiazole-Piperazine Derivatives: Involvement of Opioidergic System in the Activity

In this study, we aimed to design and synthesize novel molecules carrying both the thiazole and piperazine rings in their structures and to investigate their antinociceptive activity. Targeted compounds were obtained by reacting thiosemicarbazide derivative and appropriate 2-bromoacetophenone in ethanol. The structures of the obtained compounds were determined using data from various spectroscopic methods (IR, ¹H-NMR, ¹³C-NMR, and LCMSMS). Experimental data from in vivo tests showed that test compounds 3a–3c, 3f, and 3g (50 mg/kg) significantly prolonged reaction times of animals in tail-clip and hot-plate tests compared to the controls, indicating that these compounds possess centrally mediated antinociceptive activities. Furthermore, these compounds reduced the number of writhing behaviors in the acetic acid-induced writhing tests, showing that the compounds also possess peripheral antinociceptive activity. In the mechanistic studies, naloxone pre-treatments abolished the antinociceptive activities of compounds 3a–3c, 3f, and 3g, indicating that opioidergic mechanisms were involved in their antinociceptive effects. Molecular docking studies demonstrating significant interactions between the active compounds and µ- and δ-opioid receptor proteins supported the pharmacological findings. This study is the first showing that molecules designed to bear thiazole and piperazine moieties together on their structure exert centrally and peripherally mediated antinociceptive effects by activating the opioid system.     

Determination of Melatonin Hormone and Neurotransmitters in Cerebrospinal Fluid: Method Validation and Uncertainty Calculations

The uncertainty of measurement for well-known neurotransmitters like serotonin, noradrenalin and gamma-aminobutyric acid (GABA), glutamate and melatonin hormone with high performance liquid chromatography?fluorescence detection was calculated after the method validation. Two methods were developed for the determination of the neurotransmitters. A derivatization step was performed for the determination of GABA and glutamate. Sensitivity, method detection limit, limit of quantification, linearity, recovery, interday and intraday precision values were calculated. Low detection limit values were obtained especially for the determination of GABA and glutamate. Then, bottom-up approach was used to calculate measurement uncertainty. The critical stages of the method were evaluated. The major sources of the uncertainty budget were calibration curves, stock solution and recovery. The calculated percentage relative uncertainty values for the compounds changed between 10.1 and 16.7.     

Synthesis and anticancer activity of some novel benzothiazole-thiazolidine derivatives

Sixteen new 2-(benzothiazol-2-ylthio)-N′-(3-substituted-4-(3,4-substitutedphenyl)thiazol-2(3H)-ylidene)acetohydrazide derivatives (4a-4p) were synthesized. The structures of the synthesized compounds were elucidated using FT-IR, ¹H-NMR, ¹³C-NMR, and HRMS spectral data. Anticancer activity of the compounds 4a-4p against C6 (rat brain glioma) and A549 (human lung adenocarcinoma) cell lines was evaluated by using MTT, inhibition of DNA synthesis, and flow cytometric analysis assays. According to MTT assay, 4a and 4d were found to be the most active compounds against C6 cell line with an IC₅₀ value of 0.03 mM. Moreover, IC₅₀ values of 4a (0.2 mM) and 4d (0.1 mM) against NIH3T3 (mouse embryo fibroblast cell line) were higher than their IC₅₀ values (0.03 mM) against C6 cell line. Accordingly, selectivity of compound 4a against C6 cell line was two-fold higher than that of compound 4d. Flow cytometry analysis showed that these compounds display anticancer activity by inducing apoptosis. As a result, compound 4a has a remarkable anticancer activity and a good selectivity towards C6 cell lines.     

An improved procedure for the Beckmann rearrangement of cyclobutanones

γ-Lactams are important building blocks for the synthesis of biologically active molecules and can easily be accessed via Beckmann rearrangement of cyclobutanones. However, Beckmann fragmentation is often a competing reaction for these strained ketones. We found that performing the Beckmann rearrangement with Tamura’s reagent in the presence of aqueous HCl suppresses the undesired fragmentation reaction. This improved procedure was applied to a broad scope of substrates affording monocyclic, bicyclic, tricyclic or spirocyclic lactams.Our experimental results and DFT calculations suggest that the mechanism of the rearrangement probably involves a tetrahedral intermediate and doesn’t proceed via oxime fragmentation as in a classical Beckmann rearrangement.     

Fabrication of amperometric cholesterol biosensor based on SnO<Subscript>2</Subscript> nanoparticles and Nafion-modified carbon paste electrode

This study reports the fabrication of an amperometric cholesterol biosensor based on cholesterol oxidase (ChOx), SnO₂NPs and Nafion-modified carbon paste enzyme electrodes (CPE/SnO₂NPs-ChOx/Naf). The electrochemical characterisations of BCPE and CPE/SnO₂NPs were performed using CV and EIS. The determination of cholesterol was carried out by electrochemical oxidation of H₂O₂ at 0.6 V vs. Ag/AgCl. The CPE/SnO₂NPs-ChOx/Naf presented a linear range from 0.20 μ.mol L^?1 to 4.95 μmol L^?1 with a low limit of detection (0.04 μ.mol L^?1). In addition, the optimal values for pH and temperature were found to be 7.5 and 35°C, respectively. The CPE/SnO₂NPs-ChOx/Naf was used for the determination of cholesterol in serum samples and good results were obtained.     

Novel Thiosemicarbazone Derivatives: In Vitro and In Silico Evaluation as Potential MAO-B Inhibitors

MAO-B inhibitors are frequently used in the treatment of neurodegenerative diseases such as Parkinson’s and Alzheimer’s. Due to the limited number of compounds available in this field, there is a need to develop new compounds. In the recent works, it was shown that various thiosemicarbazone derivatives show hMAO inhibitory activity in the range of micromolar concentration. It is thought that benzofuran and benzothiophene structures may mimic structures such as indane and indanone, which are frequently found in the structures of such inhibitors. Based on this view, new benzofuran/benzothiophene and thiosemicarbazone hybrid compounds were synthesized, characterized and screened for their hMAO-A and hMAO-B inhibitory activity by an in vitro fluorometric method. The compounds including methoxyethyl substituent (2b and 2h) were found to be the most effective agents in the series against MAO-B enzyme with the IC₅₀ value of 0.042 ± 0.002 µM and 0.056 ± 0.002 µM, respectively. The mechanism of hMAO-B inhibition of compounds 2b and 2h was investigated by Lineweaver–Burk graphics. Compounds 2b and 2h were reversible and non-competitive inhibitors with similar inhibition features as the substrates. The K_i values of compounds 2b and 2h were calculated as 0.035 µM and 0.046 µM, respectively, with the help of secondary plots. The docking study of compound 2b and 2h revealed that there is a strong interaction between the active sites of hMAO-B and analyzed compound.     

Effects of solvent casted poly (lactic acid)/poly(ethylene glycol)/paraben derivative triazine films on antibacterial performance and cytotoxicity

A series of poly(lactic acid) (PLA) films that including fully paraben substituted triazine derivatives having anti-bacterial properties have been prepared by utilizing the solvent-casting method. PLA as biodegradable polymer, poly(ethylene glycol) (PEG) as a plasticizing agent and s-triazine molecules (TA01, TA02, TA03, TA04, and TA05) behaving as an anti-bacterial component have been utilized in the experiments. The influence of TA compounds on the antibacterial performance of PLA/PEG films was investigated for the first time against Gram-negative Escherichia coli (E. coli) and Gram-positive Staphylococcus aureus (S. aureus) bacteria via the contact active method. TA01-03-05 incorporated PLA/PEG films gave the best results against E.coli bacteria and log10 reductions of these films were 0.78, 0.64, and 0.65 respectively. The effect of TA compounds on the cell viability was investigated against cancer and non-cancerous cell lines using an MTS assay. The results showed that TA compounds had a positive effect on cell growth in non-cancerous cells, while they had a negative effect on cell growth in cancer cells. Furthermore, the addition of TA considerably increased the decomposition temperatures from 349° to 361° and char yield from 0.65 for PLA/PEG film to 2.3 for PLA/PEG/TA05. All of the films had good transparency and low opacity which was 7.2 for pure PLA used for control and the maximum opacity value was 11.2 observed for PLA/PEG/01. TA03 and TA04 caused a decrement of water vapor permission when compared to PLA/PEG films from 1439 to 749 and 664. It was also observed that pure PLA/PEG film lost weight rapidly over time during degradation tests. On the other hand, weight loss wasn't observed in PLA/PEG/TA films. This study focused on demonstrating the use of our new, flexible PLA/PEG derivatives in food and medical packaging.