Synthesis,Spectroscopy, X‐ray Crystallography,and DFT Computations of Nanosized Phosphazenes

Nanoparticles of nine phosphazenes with general formula 4‐CH₃C₆H₄S(O)₂N=PX₃ [X = Cl ( A ), NC₄H₈ ( 1 ), NC₆H₁₂ ( 2 ), NC₄H₈N–C(O)OC₂H₅ ( 3 ), NC₄H₈N–C(O)OC₆H₅ ( 4 ), NC₄H₈O ( 5 ), NHCH₂–C₄H₇O ( 6 ), N(CH₃)(C₆H₁₁) ( 7 ), NHCH₂–C₆H₅ ( 8 ), and 2‐NH‐NC₅H₄ ( 9 )] were synthesized using ultrasonic method and characterized by ¹H, ¹³C, ³¹P NMR, FT‐IR, fluorescence, as well as UV/Vis spectroscopy and additionally with XRD, FE‐SEM, N₂ sorption, and elemental analysis. The ³¹P NMR spectra of compounds 1 – 9 reveal the most up field shift δ(³¹P) for 9 at –11.45 ppm reflecting the most electron donation of 2‐aminopyridinyl rings through resonance to the phosphorus atom. The ¹H, ¹³C NMR spectra of 7 exhibit two sets of signals for the hydrogen and carbon atoms of its two isomers present in the solution state in 1:4 ratio. The FE‐SEM micrographs illustrate that the nanoparticles of compounds 1 – 9 have spherical morphology and a size of 27–42 nm. From the XRD patterns, the crystal sizes were estimated to about 24–86 nm. The highest bandgap was measured for 3 (3.81 eV) whereas the smallest was measured for 8 (3.50 eV). The structures of two polymorphs of compound 5 ( 5 , 5′ ) were determined by X‐ray crystallography at 120 K. Both of these polymorphs are triclinic with P1 space group but 5 has a doubled unit cell volume and two symmetrically independent molecules ( 5a and 5b ). In structures 5a and 5′ , the phosphorus and all endocyclic atoms of two morpholinyl rings display disorder, whereas the molecule 5b does not show disorder. The strong intermolecular O–H ··· O hydrogen bonds plus weak intermolecular C–H ··· O and C–H ··· N interactions create three‐dimensional polymers in the crystalline networks of 5 and 5′ . The DFT computations illustrate that molecule 5b is more stable than 5a by –1.1062 and –0.9779 kcal · mol^–1 at B3LYP and B3PW91 levels, respectively. The NBO calculations presented sp³d hybridization for phosphorus and sulfur atoms and sp², sp³ hybrids for the nitrogen and oxygen atoms.     

One‐pot Green Procedure for Synthesis of Tetrahydrobenzo[a]xanthene‐11‐one Catalyzed by Brønsted Ionic Liquids under Solvent‐free Conditions

An efficient one‐pot condensation of β‐naphthol, aldehydes and cyclic 1,3‐dicarbonyl compound has been achieved with ionic liquids as catalyst, thus a variety of 8,9,10,12‐tetrahydrobenzo[a]xanthen‐11‐one derivatives were prepared in good yields. The present approach offers several advantages such as shorter reaction times, good yields and mild reaction conditions.     

Synthesis and Characterization of Tin Oxide Nanoparticles by Solid State Chemical Reaction Method

High purity tin oxide nanopowders have been synthesized by using a solid-state chemical reaction technique with annealing at elevated temperature. The effects of two parameters, specifically by controlling the annealing temperature and kind of alkaline chlorides as precursors, the effect on particle size, morphology and IR spectra of synthesized tin oxide nanopowder were investigated. From the X-ray pattern, the crystal structure of the synthesized powders was confirmed as a tetragonal structure. Based on the recorded FTIR spectrum of SnO₂, the IR bands due to SnO₂ vibrations and its lattice modes were observed at 625 and 690 cm⁻¹, respectively. In addition, an important characterization peak has been identified at 1,450 cm⁻¹ due to Sn–O–Sn bridges observed only when LiCl was used as precursor. The formation of Sn–O–Sn bridges was confirmed by TGA–DTA analysis. According to the SEM images, it is obvious to notice that the kind of alkaline chlorides as precursors play a dominant role in controlling the morphology of tin oxide nanopowders.     

Optical and thermal behavior of novel fluorinated polyimides capable of preparing colorless, transparent and flexible films

A new diamine, 1,5-bis(2-amino-4-trifluoromethylphenoxy)naphthalene (DA1524) was synthesized by the nucleophilic substitution reaction of 1,5-dihydroxynaphthalene and 4-chloro-3-nitrobenzotrifluoride in the presence of potassium carbonate in N,N-dimethylformamide, followed by catalytic reduction with hydrazine and Pd/C in ethanol. DA1524 was then utilized to prepare a novel class of CF₃-containing polyimides. Intrinsic viscosities [η] of the polymer solutions at 25 °C were measured by the extrapolation of their viscosity numbers till zero concentration. and values of the resulting polymers were determined using gel-permeation chromatography (GPC). The polymers showed a good film-forming ability, and some characteristics of their thin films including color and flexibility were investigated qualitatively. In addition, the absorption edge values (λ₀) obtained from their UV–vis curves were determined, and all the resulting polyimides films exhibited high optical transparency. Thermal stability of the polymers was investigated using TGA analyses. The T_g values of the polyimides obtained from their DSC plots were quantified. Solubility of the samples in a variety of organic solvents was also tested.     

Profit maximization in simultaneous lot-sizing and scheduling problem

This paper extends the simultaneous lot-sizing and scheduling problem, to include demand choice flexibility. The basic assumption in most research about lot-sizing and scheduling problems is that all the demands should be satisfied. However, in a business with a goal of maximizing profit, meeting all demands may not be an optimum decision. In the profit maximization simultaneous lot-sizing and scheduling problem with demand choice flexibility, the accepted demand in each period, lot-sizing and scheduling are three problems which are considered simultaneously. In other words the decisions pertaining to mid-term planning and short-term planning are considered as one problem and not hierarchically. According to this assumption, the objective function of traditional models changes from minimizing costs to maximizing profits.     

Determination of desipramine in biological samples using liquid–liquid–liquid microextraction combined with in‐syringe derivatization,gas chromatography,and nitrogen/phosphorus detection

A method was established for the determination of desipramine in biological samples using liquid–liquid–liquid microextraction followed by in‐syringe derivatization and gas chromatography–nitrogen phosphorus detection. The extraction method was based on the use of two immiscible organic solvents. n‐Dodecane was impregnated in the pores of the hollow fiber and methanol was placed inside the lumen of the fiber as the acceptor phase. Acetic anhydride was used as the reagent for the derivatization of the analyte inside the syringe barrel. Parameters that affect the extraction efficiency (composition of donor and acceptor phase, ionic strength, sample temperature, and extraction time) as well as derivatization efficiency (amount of acetic anhydride and reaction time and temperature) were investigated. The limit of detection was 0.02 μg/L with intra and interday RSDs of 2.6 and 7.7%, respectively. The linearity of the method was in the range of 0.2–20 μg/L (r² = 0.9986). The method was successfully applied to determine desipramine in human plasma and urine.     

Characterization and optical property of ZnO nano-, submicro- and microrods synthesized by hydrothermal method on a large-scale

In the present paper, well-dispersed ZnO nano-, submicro- and microrods with hexagonal structure were synthesized by a simple low temperature hydrothermal process from zinc nitrate hexahydrate without using any additional surfactant, organic solvent or catalytic agent. The phase and structural analysis were carried out by X-ray diffraction (XRD), the morphological analysis was carried out by field emission scanning electron microscopy (FESEM) and the optical property was characterized by room-temperature photoluminescence (PL) spectroscopy. The results revealed the high crystal quality of ZnO powder with hexagonal (wurtzite-type) crystal structure and the formation of well-dispersed ZnO nano-, submicro- and microrods with diameters of about 50, 200 and 500 nm, and lengths of 300 nm, 1 μm and 2 μm, respectively, on a large-scale just using the different temperatures. Room-temperature PL spectrum from the ZnO nanorods reveals a strong UV emission peak at about 360 nm and no green emission band at ∼530 nm. The strong UV photoluminescence indicates the good crystallization quality of the ZnO nanorods. Room-temperature PL spectra from the ZnO submicro- and microrods reveal a weak UV emission peak at ∼400 nm and a very strong visible green emission at 530 nm, that is ascribed to the transition between V_oZn_i and valence band.     

Quantitation of atorvastatin in human plasma using directly suspended acceptor droplet in liquid-liquid-liquid microextraction and high-performance liquid chromatography-ultraviolet detection

A simple and sensitive methodology based on liquid-liquid-liquid microextraction (LLLME) followed by high-performance liquid chromatography-ultraviolet detection (HPLC-UV) has been successfully developed for the determination of atorvastatin (AT) in human plasma. AT was first extracted from 4.5 mL acidic aqueous sample (diluted plasma, donor phase, pH 1) at temperature 45 °C through 400 μL 1-octanol for 4.5 min, while being agitated by a stirring bar at 1250 rpm. Then, a 5.5 μL free suspended basic aqueous droplet (acceptor phase, pH 10) was delivered to the top-center position of the organic membrane. The mixture was stirred at 650 rpm for 7.5 min and the analyte was back-extracted into the droplet. Finally, the acceptor phase was taken into a microsyringe and injected directly into the HPLC. An enrichment factor of 187 along with substantial sample clean up was obtained under the optimized conditions. The calibration curve showed linearity in the range of 1-500 ng mL⁻¹ with regression coefficient corresponding to 0.996. Limits of detection (S/N = 3) and quantification (S/N = 10) were 0.4 and 1 ng mL⁻¹, respectively. A reasonable relative recovery (91%) and satisfactory intra-assay (4.4-7.0%, n = 6) and inter-assay (4.9-7.7%, n = 8) precision illustrated good performance of the analytical procedure. This technique was eventually applied for the determination of AT in human plasma after oral administration of 40 mg single dose of drug. The protocol proved to be highly cost-effective and reliable for the screening purpose.     

Synthesis and kinetic study on the thermal degradation of triblock copolymer of polycaprolactone‐poly (glycidyl nitrate)‐polycaprolactone (PCL‐PGN‐PCL) as an energetic binder

In this study, an energetic binder is synthesized via ring opening copolymerization of ε‐caprolactone with poly (glycidyl nitrate) (PGN) of low molecular weight (M_n = 1350 g mol^?1) as a macroinitiator to form triblock copolymer polycaprolactone‐PGN‐polycaprolactone (PCL‐PGN‐PCL) (M_n = 4128 g mol^?1). The effects of catalyst type and its concentration, reaction time, and solvent are investigated in this polymerization reaction. The resulting triblock copolymer is characterized by Fourier transform infrared spectroscopy (FT‐IR), nuclear magnetic resonance spectroscopy (NMR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and thermal gravimetric analysis (TGA). The DSC result shows that the glass transition temperature of triblock copolymer (T_g = ?50°C) is lower than PGN (T_g = ?35°C). Also, the decomposition kinetics of this energetic binder is studied by DSC, TGA, and its derivative (DTG). An advanced isoconversional method is applied for kinetic analysis. Activation energy is calculated by Flynn‐Wall‐Ozawa (FWO) and Kissinger methods. The resulting activation energy from Kissinger method for the first and the second steps are 42.98 and 74.56 kJ mol^?1, respectively. Also, it is found from FWO results that the activation energy for the copolymer increases with degradation degree (α).     

A novel nano‐cotton‐like bismuth oxyfluoride (NC‐BiOF) and a novel nanosheet heterogeneous compound BiOF@ZIF‐8 as catalyst for the selective and green oxidation of benzylic alcohols

We describe here for the first time a new morphology of BiOF nanoparticles with a cotton‐like structure, made using a hydrothermal synthesis method. We also prepared heterogeneous nanosheets of BiOF@ZIF‐8 by a one‐pot synthesis under hydrothermal conditions. We demonstrate that in this method the morphology of BiOF and one‐pot synthesis conditions are the main factors for the preparation of the nanosheet BiOF@ZIF‐8. Fourier transform infrared (FTIR), X‐ray diffraction (XRD), scanning electron microscopy (SEM), energy‐dispersive X‐ray (EDX), thermogravimetry‐differential thermal analysis (TG‐DTA), and BET surface area were used to characterize the samples prepared. XRD, SEM, and adsorption–desorption analysis showed that the structure of ZIF‐8 and BiOF form intact only in one‐pot synthesis of BiOF (with nano‐cotton‐like morphology) with Zn(NO₃)₃, while spectral techniques show the successful encapsulation of the sheet BiOF on ZIF‐8. Nanosheet BiOF@ZIF‐8 was found to be a highly efficient heterogeneous catalyst for the selective oxidation of alcohols. BiOF@ZIF‐8 could be reused several times although it got less active with recycling.