Minimizing Side Product Formation in Alkyne Functionalization of Ruthenium Complexes by Introduction of Protecting Groups

The synthesis of alkyne functionalized bipyridine ruthenium complexes are reported. The improved synthetic approach through application of stable protecting groups prevents formation of possible side products while facilitating purification. By applying copper-catalysed azide-alkyne cycloaddition reactions (CuAAC) pyrene units with flexible alkyl linkers are introduced at the periphery of the complex, opening up various applications including surface immobilization and DNA intercalation. All complexes are characterized structurally as well as photophysically, especially regarding the influence of the introduced alkyne and triazolyl substituents on their photophysical behavior.     

The Pharmacokinetic Profiles of Pre-Operative Prophylactic Cefepime Application in Pregnant and Non-Pregnant Women Undergoing Surgical Interventions Using a Fully Validated Liquid Chromatographic Method

Pregnancy alters pharmacokinetic profile of many drugs, because of altering body volume and metabolism rate. Therefore, dosage rates and concentrations of drugs must be controlled during pregnancy. Here, we identified the pharmacokinetic profile of pre-operatively given cefepime in caesarean section and gynecological operations using a simple, rapid, cost-effective and valid liquid chromatographic method. The chromatographic separation was performed using 40 mM, pH 3.2 phosphate buffer containing 6 % methanol as mobile phase at 0.30 mL min^?1 flow rate. Gradient elution with methanol was applied to get shorter analysis time without any interference from plasma endogens. During analyses, temperature of column, autosampler and detector were set as 30, 10 and 40 °C, respectively. The detection wavelength was 260 nm and ceftizoxime was used as internal standard. At the optimum conditions, the cefepime analysis from plasma samples was completed in 7 min. Cefepime was extracted from plasma samples using perchloric acid with a very high recovery rate (99.3 %). The method was fully validated according to the Food and Drug Administration guidelines for bioanalytical method validation, and found to be selective, linear, repeatable, reproducible and robust. After validation studies, the method was applied to five caesarean-sectioned and four non-pregnant sectioned women treated with pre-operative, prophylactic single intravenous dose of cefepime (1 g Maxipime^®) in order to determine pharmacokinetic profile of cefepime. Peak serum concentrations of cefepime in caesarean-sectioned women at the arterial port after infusion was 70.11 ± 10.74 μg mL^?1. The mean elimination half-life, volume of distribution and calculated area under the concentration–time curve (AUC)_0–∞ were 1.10 ± 0.23 h, 14.22 ± 2.29 L and 101.55 ± 10.99 μg h mL^?1 for caesarean-sectioned women; and 1.14 ± 0.21 h, 14.76 ± 2.92 L and 104.71 ± 36.34 μg h mL^?1 for non-pregnant sectioned women, respectively. The area under curve, elimination half-life, maximum plasma concentration and the mean distribution volume of cefepime were not changed in case of pregnancy.     

Effect of 0h11/2 Level on Shell Model Calculations of ^105Sb and ^107Sb

The full and reduced shell model calculations have been carried out for the light odd-even ^105Sb and ^107Sb isotopes. The model space has been chosen as 1d5/2, 0g7/2, 1d3/2, 2s1/2, and 0h11/2 for the full calculations and excluded 0h11/2 for the reduced calculations. The reduced shell model calculations of ^105Sb and ^107Sb isotopes are presented for the first time. We obtain the energy spectra for the ^105Sb and ^107Sb isotopes in the full and reduced model space by using CD-Bonn two-body effective nucleon-nucleon interaction. The resulting energy spectra are compared to the experimental results to understand the effect of the 0h11/2 level on the shell model calculations. We draw conclusions about the right model space in the shell model calculations for the isotopes around the N =Z= 50 region of the periodic table.     

Uranium enrichment measurements using the intensity ratios of self-fluorescence X-rays to 92 keV gamma ray in UXKα spectral region

In this paper, the known multigroup γ-ray analysis method for uranium (MGAU) as one of the non-destructive γ-ray spectrometry methods has been applied to certified reference nuclear materials (depleted, natural and enriched uranium) containing ²³⁵U isotope in the range of 0.32-4.51% atom ²³⁵U. Its analysis gives incorrect results for the low component ²³⁵U in depleted and natural uranium samples where the build-up of the decay products begins to interfere with the analysis. The results reveal that the build-up of decay products seems to be significant and thus the algorithms for the presence of decay products should be improved to resulting in the correct enrichment value. For instance, for the case of ²³⁵U analysis in depleted uranium or natural ore samples, self-induced X-rays such as 94.6 keV and 98.4 keV lying in UXK_α spectral region used by MGAU can be excluded from the calculation. Because the significant increases have been observed in the intensities of uranium self-induced X-rays due to γ-ray emissions with above 100 keV energy arising from decay products of ²³⁸U and ²³⁵U and these parents. Instead, the use of calibration curve to be made between the intensity ratios of self-fluorescence X-rays to 92^* keV γ-ray and the certified ²³⁵U abundances is suggested for the determination of ²³⁵U when higher amounts of decay products are detected in the γ-ray spectrum acquired for the MGAU analysis.     

La3Ni2O6: a new double T'-type nickelate with infinite Ni1+/2+O2 layers

New mixed-valent, Ni1+/Ni2+, metastable nickelate, La3Ni2O6, was synthesized by low-temperature reduction of La3Ni2O7 with CaH2. The crystal structure of La3Ni2O6 (space group: I4/mmm, a = 3.9686(1) A and c = 19.3154(6) A) was determined from powder neutron diffraction data by Rietveld analysis. The structure can be described as an intergrowth of LaO2 fluorite and double infinite layer (LaNiO2)2 blocks and represents the n = 2 homologue of the T'-type series Lan+1NinO2n+2. Such double T'-type structural arrangement has never been observed before. The 3d9/3d8 electronic configuration of Ni1+/Ni2+ and the presence of NiO2 infinite layers resemble electronic and structural features of the superconducting cuprates. X-ray absorption spectroscopy supports the 1+/2+ oxidation state and planar coordination of Ni in agreement with the structure determination.     

Investigation of equilibrium, kinetic, thermodynamic and mechanism of Basic Blue 16 adsorption by montmorillonitic clay

The adsorption of a cationic dye, Basic Blue 16 (BB16), by montmorillonitic clay was studied in detail. Changes in the molecular structure during adsorption were analyzed by FTIR spectroscopy. BB16 adsorption onto the clay mainly results from hydrogen bonding between OH and NH₂ groups of dye molecules and OH groups of clay and electrostatic interaction between the negatively charged clay surface and cationic dye. The montmorillonitic clay dose had an inverse effect on the adsorption performance, while the highest dye removal was 305 mg/g at pH 3.6. An increase in temperature and dye concentration positively enhanced the adsorption capacity of the montmorillonitic clay. Temperature had no effect on the adsorption at a dye concentration less than 500 mg/L, while dye adsorption was positively enhanced at elevated dye concentrations. Three-parameter equations provided higher better fitting than two-parameter equations while the Freundlich model had the highest correlation coefficient and the lowest error values with experimental data. The BB16 adsorption was well followed by pseudo-second order model and the rate of adsorption process was controlled by surface and intraparticle diffusion. Thermodynamic evaluations revealed that the adsorption process was spontaneous and endothermic, while the randomness increased during adsorption. Experimental results indicate that montmorillonitic clay from Eskisehir is a promising adsorbent for the removal of cationic dye molecules from aqueous solutions.     

The impact of an out‐of‐school STEM education program on students’ attitudes toward STEM and STEM careers

There is an increasing awareness of out‐of‐school program value in enhancing student interest and understanding of science, technology, engineering, and mathematics (STEM). This study examined the impact of an out‐of‐school STEM education program on student attitudes toward STEM disciplines and STEM careers. A STEM education program implemented at a public research university was designed to integrate STEM disciplines with hands‐on problem‐based activities. Design features included authentic learning contexts, engineering design processes, and content integration. Data sources included an attitude survey and interviews conducted with forty sixth grade middle school student participants. The analysis revealed significant differences between pre and posttests on student attitudes toward personal and social implications of STEM, science and engineering learning, and their relationship to STEM. Findings showed that the program contributed to students’ developing interest in STEM fields, and helped them make connections between schoolwork and daily lives. Recommendations for future research on out‐of‐school STEM education programs were discussed.     

Effects of hydrochloric acid treatment on structure characteristics and C<Subscript>2</Subscript>H<Subscript>4</Subscript> adsorption capacities of Ünye bentonite from Turkey: a combined FT-IR,XRD, XRF,TG/DTA and MAS NMR study

In this study, a bentonite sample from Ünye, Turkey was treated with various HCl solutions (0.1, 1.0 and 5.0 M) at 90 °C during 3 and 6 h. X-ray diffraction (XRD), X-ray fluorescence (XRF), differential thermal analysis (DTA), thermogravimetric analysis (TG), Fourier transform infrared (FT-IR), magic angle spinning nuclear magnetic resonance (²⁹Si and ²⁷Al MAS NMR) and surface area measurement methods were employed in order to investigate the structural and thermal changes occurring as a result of the acid activation. The data for the adsorption of C₂H₄ obtained at 273 K and pressures up to 100 kPa correlated with structural properties of the acid treated bentonite samples. With the increase of both concentration of acid solution and treatment time, the specific surface area values and the retentions of C₂H₄ gas of bentonite samples increased. Bentonite treated with 5.0 M HCl for 6 h adsorbed C₂H₄ most effectively.     

2H-Indazolo[2,1-b]phthalazine-trione derivatives: Inhibition on some metabolic enzymes and molecular docking studies

In this study, substituted 2H-indazolo[2,1-b]phthalazine-1,6,11-trione compounds ( 4a–d ) obtained via one-pot three-component condensation reaction of aromatic aldehydes, cyclic 1,3-dione, and phthalhydrazide in ethanol catalyzed by Y(OTf)₃ showed satisfactory inhibitory effects against some important enzymes. Also, these molecules had K_i values in the row of 185.92 ± 36.03-294.82 ± 50.76 nM vs carbonic anhydrase I (CA I), 204.93 ± 46.90-374.10 ± 83.63 nM against human CA II, 937.16 ± 205.82-1021.83 ± 193.66 nM against α-glycosidase (α-Gly), respectively. For cholinesterase enzymes, the K_i values were found in the range of 47.26 ± 9.62-72.05 ± 19.47 nM against acetylcholinesterase (AChE) and 65.03 ± 9.88-102.83 ± 25.04 nM against butyrylcholinesterase (BChE), respectively. The inhibition effects of these compounds against enzymes whose name are AChE, BChE, α-Gly, hCA I, and hCA II, were compared with control molecules like tacrine, acarbose, and acetazolamide.