ZnO/Fe3O4 nanoparticles promoted green synthesis of pyrazolo pyrimidinones: Study of antioxidant activity

The preparation of pyrazolo pyrimidinone derivatives was performed by using five component reactions of phthalaldehyde, cyanomethylamine, electron deficient acetylenic compounds, isocyanate, hydrazine, and catalytic amounts of ZnO/Fe₃O₄-magnetic nanoparticles as a high performance catalyst under ultrasonic conditions at ambient temperature in aquause media at room temperature. It should be mentioned that this catalyst was prepared using Spinacia oleracea water extract. In addition, for investigation of antioxidant ability, radical trapping by DPPH and reducing power of ferric ion experiments was performed. As a result, synthesized compounds show excellent radical trapping by DPPH and good reducing ability of ferric ion. The current procedure has the benefits for instance excellent yield of reaction, green media, and easy separation of product and catalyst.     

Ultra-trace determination of arsenic species in environmental waters,food and biological samples using a modified aluminum oxide nanoparticle sorbent and AAS detection after multivariate optimization

We describe a simple and efficient method for solid phase extraction and speciation of trace quantities of arsenic. It is based on the use of functionalized aluminum oxide nanoparticles and does not require any oxidation or reduction steps. The experimental parameters affecting extraction and quantitation were optimized using fractional factorial design methods. Adsorbed arsenic was eluted from the sorbent with 1 M hydrochloric acid and determined by graphite furnace atomic absorption spectrometry. Preconcentration factors up to 750 were achieved depending on the sample volume. Studies on potential interferences by various anions and cations showed the method to be highly selective. Under optimum conditions, the calibration plots are linear in the 5.0 to 280 ng L⁻¹ and 8.0 to 260 ng L⁻¹ concentration ranges for As(III) and total arsenic, respectively. The detection limits (calculated for S/N ratios of 3) are 1.81 and 1.97 ng L⁻¹ for As(III) and total arsenic, respectively. The method was successfully applied to the determination and speciation of arsenic in (spiked) environmental, food and biological samples and gave good recoveries. The method was validated using a certified geological reference material.

Novel functionalized Al₂O₃ nanoparticles were synthesized and used for speciation and determination of arsenic in different samples. The experimental variables were optimized using fractional factorial design that can save time and operational costs.

     

Analysis of tamoxifen and its main metabolites in plasma samples of breast cancer survivor female athletes: Multivariate and chemometric optimization

A sensitive method based on liquid chromatography combined with a diode array detector was developed and validated to simultaneously determine tamoxifen, and its active metabolites N-desmethyltamoxifen, 4-hydroxytamoxifen, and endoxifen in human plasma samples. The green and sustainable vortex-assisted dispersive liquid-phase microextraction technique based on the natural hydrophobic deep eutectic solvent was used for the extraction and preconcentration of the analytes. Chemometrics and multivariate analysis were used to optimize the independent variables including the type and volume of deep eutectic solvent, extraction time, and ionic strength. Under optimal conditions, calibration curves were linear in a suitable range with the lower limits of quantification (0.8–10.0 μg/L), which covered the relevant concentrations of the analytes in plasma samples for a clinical study. Intra- and interday precision evaluated at three concentrations for the analytes were lower than 8.2 and 12.1%, respectively. Accuracy was in the range of 94.9–104.7%. The applicability of the developed method on human plasma samples illustrated the range 45.1–72.8, 98.4–128.3, 0.9–1.2, and 2.7–6.1 μg/L for tamoxifen, N-desmethyltamoxifen, 4-hydroxytamoxifen, and endoxifen, respectively. The validated method can be effective for the pharmacokinetics, pharmacodynamics, and therapeutic drug monitoring studies of tamoxifen and its main metabolites in biological fluids.     

Truthful mechanism design via correlated tree rounding

A powerful algorithmic technique for truthful mechanism design is the maximal-in-distributional-range (MIDR) paradigm. Unfortunately, many such algorithms use heavy algorithmic machinery, e.g., the ellipsoid method and (approximate) solution of convex programs. In this paper, we present a correlated rounding technique for designing mechanisms that are truthful in expectation. It is elementary and can be implemented quickly. The main property we rely on is that the domain offers fractional optimum solutions with a tree structure. In auctions based on the generalized assignment problem, each bidder has a publicly known knapsack constraint that captures the subsets of items that are of value to him. He has a private valuation for each item and strives to maximize the value of assigned items minus payment. For this domain we design a truthful 2-approximate MIDR mechanism for social welfare maximization. It avoids using the ellipsoid method or convex programming. In contrast to some previous work, our mechanism achieves exact truthfulness. In restricted-related scheduling with selfish machines, each job comes with a public weight, and it must be assigned to a machine from a public job-specific subset. Each machine has a private speed and strives to maximize payments minus workload of jobs assigned to it. Here we design a mechanism for makespan minimization. This is a single-parameter domain, but the approximation status of the optimization problem is similar to unrelated machine scheduling: The best known algorithm obtains a (non-truthful) 2-approximation for unrelated machines, and there is 1.5-hardness. Our mechanism matches this bound with a truthful 2-approximation.     

Applying Unconventional Spectroscopies to the Single-Molecule Magnets,Co(PPh3)2X2 (X=Cl,Br, I): Unveiling Magnetic Transitions and Spin-Phonon Coupling

Large separation of magnetic levels and slow relaxation in metal complexes are desirable properties of single-molecule magnets (SMMs). Spin-phonon coupling (interactions of magnetic levels with phonons) is ubiquitous, leading to magnetic relaxation and loss of memory in SMMs and quantum coherence in qubits. Direct observation of magnetic transitions and spin-phonon coupling in molecules is challenging. We have found that far-IR magnetic spectra (FIRMS) of Co(PPh₃)₂X₂ ( Co-X ; X=Cl, Br, I) reveal rarely observed spin-phonon coupling as avoided crossings between magnetic and u-symmetry phonon transitions. Inelastic neutron scattering (INS) gives phonon spectra. Calculations using VASP and phonopy programs gave phonon symmetries and movies. Magnetic transitions among zero-field split (ZFS) levels of the S=3/2 electronic ground state were probed by INS, high-frequency and -field EPR (HFEPR), FIRMS, and frequency-domain FT terahertz EPR (FD-FT THz-EPR), giving magnetic excitation spectra and determining ZFS parameters (D, E) and g values. Ligand-field theory (LFT) was used to analyze earlier electronic absorption spectra and give calculated ZFS parameters matching those from the experiments. DFT calculations also gave spin densities in Co-X , showing that the larger Co(II) spin density in a molecule, the larger its ZFS magnitude. The current work reveals dynamics of magnetic and phonon excitations in SMMs. Studies of such couplings in the future would help to understand how spin-phonon coupling may lead to magnetic relaxation and develop guidance to control such coupling.     

Modification of the Scaled Particle Theory for Solubility of Non-Polar Gases in Water

In this work based on the modified scaled particle theory (SPT), the solubility of non-polar gases (He, Ar, N₂, H₂, O₂, CO₂ and CH₄) in water has been studied over a wide range of temperatures. Calculations of Henry’s law constant by the SPT are related to the inherent physical properties and parameters of solvent and solute, all of which are considered temperature dependent. The temperature dependence of molar volume and hard sphere diameter of solvent and polarizability of solute have the most significant effects on the solubilities of gases in water. The average relative deviation is less than 3 %. Also, the effect of different mixing rules in the application of SPT to prediction of gas solubility has been studied.     

Adsorptive Stripping Voltammetric Determination of Imipramine and Amitriptiline at a Nanoclay Composite Carbon Ionic Liquid Electrode

A new carbon nanocomposite electrode has been designed by incorporation of montmorillonite nanoclay into a carbon ionic liquid electrode for the electrochemical determination of imipramine (IMP) and amitriptyline (AMT). They are expected to accumulate on the electrode surface through the cooperative interaction of ionic liquid and clay with the drugs. The proposed electrode also possesses attractive electrocatalytic effects towards the drugs especially AMT. Low detection limits of 19 nM for IMP and 24 nM for AMT were achieved. The proposed nanocomposite electrode exhibits good applicability for monitoring IMP and AMT in pharmaceutical formulations and blood serum samples.     

Development of a Novel Electrochemical Biosensor for Detection and Discrimination of DNA Sequence and Single Base Mutation in dsDNA Samples Based on PNA‐dsDNA Hybridization – a new Platform Technology

In spite of the extensive attention paid on the development of various DNA detection strategies, very few studies have been reported regarding direct detection of DNA sequence and mutation in dsDNA. Here, we describe the feasibility of detection and discrimination of target DNA sequences and single base mutations (SBM) directly in double‐stranded oligonucleotides and PCR products without the need for denaturation of the target dsDNA samples. This goal was achieved by employing a peptide nucleic acid (PNA) chain, self‐assembled on the gold electrode as a probe, which binds to dsDNA and forms PNA‐dsDNA hybrid.