High‐Efficiency Perovskite Solar Cells Enabled by Anatase TiO2 Nanopyramid Arrays with an Oriented Electric Field

One‐dimensional (1D) nanostructured oxides are proposed as excellent electron transport materials (ETMs) for perovskite solar cells (PSCs); however, experimental evidence is lacking. A facile hydrothermal approach was employed to grow highly oriented anatase TiO₂ nanopyramid arrays and demonstrate their application in PSCs. The oriented TiO₂ nanopyramid arrays afford sufficient contact area for electron extraction and increase light transmission. Moreover, the nanopyramid array/perovskite system exhibits an oriented electric field that can increase charge separation and accelerate charge transport, thereby suppressing charge recombination. The anatase TiO₂ nanopyramid array‐based PSCs deliver a champion power conversion efficiency of approximately 22.5 %, which is the highest power conversion efficiency reported to date for PSCs consisting of 1D ETMs. This work demonstrates that the rational design of 1D ETMs can achieve PSCs that perform as well as typical mesoscopic and planar PSCs.     

Synthesis of magnetically modified mesoporous nanoparticles and their application in simultaneous determination of Pb(II), Cd(II) and Cu(II)

In this study, a novel adsorbent from a mesoporous family (MCM-41) coating with CoFe₂O₄ and piperazine was synthesized by a simple and easy route. Its application for simultaneous preconcentration of three heavy metals including lead, cadmium and copper in real samples followed by a flame atomic absorption spectroscopy was investigated. The central composite design was employed for investigating the most effective factors of pH, amount of adsorbent, the equilibrium time and their interactions. Under the optimum conditions, the detection limits for lead, cadmium and copper were 0.50, 0.30 and 0.25 μg L^?1, respectively, and the preconcentration factor (PF) was 33. The presented method was successfully employed for the simultaneous determination of the three mentioned heavy metals in real samples with recoveries of 90%–105%. The accuracy of the suggested methods was also investigated through spiking samples and a reasonable range for recoveries from 90.3% to 107% was acquired. The isotherm models and thermodynamic parameters have also been studied. The new adsorbent showed fast adsorption kinetics within 10 min and maximum Langmuir monolayer capacities of 238.09, 178.57 and 208.33 mg g^?1 for lead, cadmium and copper, respectively.     

Preparation of a novel iodide-selective electrode based on iodide-miconazole ion-pair and its application to pharmaceutical analysis.

An iodide-miconazole ion-paired complex was used as a suitable ion-exchanger for the preparation of a plasticized-PVC membrane electrode. Among different solvent mediators tested, dioctylsebacate exhibited the proper response characteristics, including Nernstian slope of the calibration curve, fast response time and good reproducibility of the emf values. The electrode exhibits a Nernstian slope of -59.8 +/- 0.5 mV decade(-1) for I- ion over a concentration range of 1.0 x 10(-5) - 1.0 x 10(-2) M with a limit of detection of 7.0 x 10(-6) M. The electrode displays a good selectivity for I- with respect to a number of inorganic and organic species. It canbe used over a pH range of 2.5 - 8.5. The membrane sensor was successfully applied to the determination of iodide in water samples and blood serum, as well as in pharmaceutical products such as iodoquinol and thyroxin.     

Fluorimetric Determination of Gentamicin in Dosage Forms and Biological Fluids Through Derivatization with 4-Chloro-7-Nitrobenzo-2-Oxa-1,3-Diazole (NBD-Cl)

 A highly sensitive fluorimetric method has been developed for the determination of gentamicin. The method is based on its coupling with 4-chloro-7-nitrobenzo-2-oxa-1,3-diazole (NBD-Cl) in 50% (v/v) methanolic phosphate buffer (pH 7.2) to give an intensely fluorescent product having excitation and emission wavelengths at 465 nm and 530 nm, respectively. The experimental parameters were carefully studied and incorporated into the procedure. The fluorescence-concentration plot is rectilinear over the range 0.56–2.8 μg/mL (r = 0.999) with minimum detectability (S/N = 2) of 0.11 μg/mL (1.6 × 10⁻⁷ mol/L). The method was applied successfully to the determination of the drug in pharmaceutical dosage forms and the percentage recoveries were satisfactorily accurate and precise. The method was further applied to spiked human plasma samples, the percentage recovery was 97.9 ± 3.4. The interference encountered from endogenous amino acids could be eliminated through selective complexation with freshly prepared copper (II) hydroxide. A proposal of the reaction pathway is presented. The method can measure the intact drug, and can be used in presence of possible interference. Received April 18, 2001; accepted April 10, 2002     

Crystal structure of palladium(II) complex with 2,2′-dipyridylamine and 4-toluenesulfonyl-L-serine

The [Pd(dpa)(tsser)] complex (1) is prepared from the reaction of PdCl₂ and 2,2′-dipyridylamine (dpa) with 4-toluenesulfonyl-L-serine (tsserH₂). This complex is characterized by spectral methods (IR, UV-Vis, ¹H NMR, and luminescence), elemental analysis, thermal analysis (TG, DTA), and single crystal X-ray diffraction. X-ray structure determinations show that in this complex, Pd^II atoms are four-coordinated in a distorted square-planar configuration by two N atoms from a bidentate 2,2′-dipyridylamine ligand and one N atom and one O atom from a bidentate tsser^2– ligand.     

Preparation and investigation of tribological properties of ultra‐high molecular weight polyethylene (UHMWPE)/graphene oxide

This article has been devoted to investigation of the tribological properties of ultra‐high molecular polyethylene/graphene oxide nanocomposite. The nanocomposite of ultra‐high molecular polyethylene/graphene oxide was prepared with 0.5, 1.5, and 2.5 wt% of graphene oxide and with a molecular weight of 3.7 × 10⁶ by in‐situ polymerization using Ziegler–Natta catalyst. In this method, graphene oxide was used along with magnesium ethoxide as a novel bi‐support of the Ziegler–Natta catalyst. Analyzing the pin‐on‐disk test, the tribological properties of the nanocomposite, such as wear rate and mean friction coefficient, were investigated under the mentioned contents of graphene oxide. The results showed that an increase in graphene oxide content causes a reduction in both wear rate and mean coefficient friction. For instance, by adding only 5 wt% graphene oxide to the polymeric matrix, the wear rate and mean coefficient friction decreased about 34% and 3.8%, respectively. Also, the morphological properties of the nanocomposite were investigated by using X‐ray diffraction and scanning electron microscopy. In addition, thermal properties of the nanocomposite were analyzed using differential scanning calorimetry, under various contents of graphene oxide. The results of the morphological test indicated that the graphene oxide was completely exfoliated into the polymeric matrix without any agglomeration. Copyright © 2016 John Wiley & Sons, Ltd.     

Zinc(II) complexes of 4-aminoantipyrine (AAP). Crystal structure of [Zn(AAP)<Subscript>2</Subscript>Cl<Subscript>2</Subscript>]

Zinc(II) complexes of 4-aminoantipyrine (AAP), [Zn(AAP)₂X₂] (X = Cl^–, I^–) and [Zn(AAP)(CN)₂] · 2H₂O were prepared and characterized by elemental analysis, IR and NMR (¹H & ¹³C) spectroscopy. The crystal structure of [Zn(AAP)₂Cl₂] (1) was determined by X-ray crystallography. The structural analysis of 1 shows that the complex exists as a monomeric nonionic molecule with zinc atom bound to two AAP ligands and two chloride ions adopting a distorted tetrahedral geometry. In [Zn(AAP)₂(CN)₂] · 2H₂O, the appearance of a band at 2162 cm^–1 in IR and resonances around 142 ppm in the ¹³C NMR spectra indicated the binding of cyanide to zinc(II).     

Quantification of sofosbuvir in human serum by liquid chromatography with negative ionization mass spectrometry using the parent peak and its source‐induced fragment: Application to a bioequivalence study

In the mass spectrometry of sofosbuvir, a new orally administered antihepatitis C drug, a weak peak is detected at the m/z value of the parent ion (m/z 530) as a result of in‐source dissociation and current methods to its quantification, is based on monitoring of the parent peak using ultra high‐performance liquid chromatography with tandem mass spectrometry. With these methods serum concentration of the drug is quantifiable only up to 4–5 h postdose. However, the fragmentation of the molecule generates a more stable ion at m/z 287 (base peak) with a signal intensity of about tenfold compared to the parent ion. Our study was aimed to improve sensitivity of analysis by acquisition of the m/z value of the daughter ion from which it originated instead of the parent molecule. This novelty allows us to measure serum concentrations of the drug for a longer time postdose and provides more opportunity for pharmacokinetic studies of sofosbuvir. Our method was linear over the concentration range of 2–2560 ng/mL of sofosbuvir in human serum with a limit of quantification of 2 ng/mL compared to 10 ng/mL reported previously. The coefficient variation values of both inter and intraday analysis were less than 13.8%, and the percentage error was less than 6.3.     

Functionalized nanoparticles based solid‐phase membrane micro‐tip extraction and high‐performance liquid chromatography analyses of vitamin B complex in human plasma

Iron nanoparticles were prepared by a green method following functionalization using 1‐butyl‐3‐methylimidazolium bromide. 1‐Butyl‐3‐methylimidazole iron nanoparticles were characterized using FTIR spectroscopy, energy dispersive X‐ray fluorescence, X‐ray diffraction, scanning electron microscopy and transmission electron microscopy. The nanoparticles were used in solid‐phase membrane micro‐tip extraction to separate vitamin B complex from plasma before high‐performance liquid chromatography. The optimum conditions obtained were sorbent (15 mg), agitation time (30 min), pH (9.0), desorbing solvent [water (5 mL) + methanol (5 mL) + sodium hydroxide (0.1 N) + acetic acid (d = 1.05 kg/L, pH 5.5), desorbing volume (10 mL) and desorption time (30 min). The percentage recoveries of all the eight vitamin B complex were from 60 to 83%. A high‐performance liquid chromatography method was developed using a PhE column (250 × 4.6 mm, 5.0 μm) and water/acetonitrile (95:5, v/v; pH 4.0 with 0.1% formic acid) mobile phase. The flow rate was 1.0 mL/min with detection at 270 and 210 nm. The values of the capacity, separation and resolution factor were 0.57–39.47, 1.12–6.00 and 1.84–26.26, respectively. The developed sample preparation and chromatographic methods were fast, selective, inexpensive, economic and reproducible. The developed method can be applied for analyzing these drugs in biological and environmental matrices.     

NO and OH* emission characteristics of very-lean to stoichiometric ammonia–hydrogen–air swirl flames

One of the main concerns regarding ammonia combustion is its tendency to yield high nitric oxide (NO) emissions. Burning ammonia under slightly rich conditions reduces the NO mole fraction to a low level, but the penalties are poor combustion efficiency and unburnt ammonia. As an alternative solution, this paper reports the experimental investigation of premixed swirl flames fueled with ammonia-hydrogen mixtures under very-lean to stoichiometric conditions. A gas analyzer was used to measure the NO mole fraction in the flame and post flame regions, and it was found that low NO emissions (as low as 100 ppm) in the exhaust were achieved under very lean conditions (? ≈ 0.40). Low NO emission was also possible at higher equivalence ratios, e.g. ? = 0.65, for very large ammonia fuel fractions (X_NH3 > 0.90). 1-D flame simulations were performed to elaborate on experimental findings and clarify the observations of the chemical kinetics. In addition, images of OH* chemiluminescence intensity were captured to identify the flame structure. It was found that, for some conditions, the OH* chemiluminescence intensity can be used as a proxy for the NO mole fraction. A monotonic relationship was discovered between OH* chemiluminescence intensities and NO mole fraction for a wide range of ammonia-hydrogen blends (0.40 < ? < 0.90 and 0.25 < X_NH3 < 0.90), making it possible to use the low-cost OH* chemiluminescence technique to qualify NO emission of flames fueled with hydrogen-enriched ammonia blends.