Polymerization Effects on the Decomposition of a Pyrazolo-Triazine at high Temperatures and Pressures

4-amino-3-aminopyrazole-8-trinitropyrazolo-[5, 1-c] [1, 2, 4]triazine (PTX, C₅H₂N₈O₆) has good detonation performance, thermal stability and low mechanical sensitivity, which endow it with good development prospects in insensitive ammunition applications. To study the effects of polymerization on the decomposition of PTX, the reaction processes of PTX at different conditions were simulated by quantum chemistry and molecular dynamics methods. In this paper, the effects of polymerization on the decomposition of PTX were studied in terms of species information, reaction path of PTX, bond formation and bond cleavage, evolution of small molecules and clusters, and kinetic parameters at different stages. The results show that under the high-temperature and high-pressure conditions, the initial reaction path of unimolecular PTX in the thermal decomposition is mainly the cleavage of C−NO₂ bonds. At the same time, there are many polymerization reactions in thermal decomposition process, which may greatly affect the reaction rate and path. The higher the degree of polymerization, the larger equilibrium value of potential energy, the less energy release of thermal decomposition. Compared with the activation energy of other explosives, the activation energy of PTX is higher than that of β-HMX and lower than that of TNT.     

Synthesis,structure, characterization and biological evaluation of 3‐substituted 1‐pyridin‐2‐ylimidazo[1,5‐a]pyridine‐based copper(I)–phosphine complexes for anticancer drug screening

Copper(I) complexes of the types [Cu(N–N)(PPh₃)₂]NO₃ (LC41–LC44) and [Cu(N–N)(PPh₃)(NO₃)] (LC45) carrying 3‐substituted 1‐pyridine‐2‐ylimidazo[1,5‐a]pyridine (N–N) derivatives and triphenylphosphine (PPh₃) ligands have been prepared. The synthesized copper(I)–phosphine complexes were fully characterized by NMR, IR, ESI‐MS and UV–visible spectroscopy as well as by cyclic voltammetry. Selected structures such as LC42, LC43 and LC45 were additionally analysed by single‐crystal X‐ray method, which show that copper(I) centre adopts a highly distorted tetrahedral geometry. The ¹H and ¹³C NMR spectral data of the complexes throw light on the nature of metal–ligand bonding. They display dπ–π* metal‐to‐ligand charge transfer (MLCT) transition and show quasireversible Cu^I/Cu^II metal oxidation. Among the copper(I)–phosphine complexes, LC41–LC44 exhibit moderate cytotoxicity (IC₅₀: 24 h, 67–74 μM; 48 h, 58–70 μM) against human lung epithelial adenocarcinoma A549 cells, whereas LC45 displays the best activity (IC₅₀: 24 h, 42 μM; 48 h, 34 μM) for A549 cancer cell line, which is better than that of the commercial antitumor drug cisplatin. All the complexes also displayed excellent selectivity by being relatively inactive against the human lung epithelial L132 normal cell line with selectivity index (SI) values ranging from 3.4 to 7.4. The complexes block cell cycle progression of A549 cells in G₀/G₁ phase. FACSVerse analyses are suggestive of reactive oxygen species (ROS) generation and apoptotic cell death induced by the LC41, LC43 and LC45. The induction of apoptosis in A549 cells was shown by Annexin V with propidium iodide (PI) and 4′,6‐diamidino‐2‐phenylindole (DAPI) staining methods and established the ability of LC41, LC43 and LC45 to accumulate in the cell nuclei.     

Reduction reactions of the metallocene complex (η-C5H4CMe2C9H7)2ZrCl2

The preparation and characterization of the substituted bis(cyclopentadienyl) zirconium dichloride complexes (η⁵-C₅H₄CMe₂C₉H₇)₂ZrCl₂ (1a, b) is reported. The isomer mixture of 1a, b was treated with different reducing agents such as sodium and n-butyllithium under various reaction conditions. In these reactions CC and CH activation and cleavage reactions were observed. In combination with methylaluminoxane (MAO) 1a, b and 3 showed low activities as homogeneous ethylene polymerization catalysts and no activities towards propylene. Compounds 2 and 3 were characterized by NMR spectroscopy and X-ray crystallography.     

Sequential injection spectrophotometric assay of bromazepam complexed with iron(II) in hydrochloric acid with chemometric optimization

A sequential injection spectrophotometric method for the assay of bromazepam anxiolytic drug has been reported. The method is based on the complexation reaction of bromazepam with iron(II) in hydrochloric acid media and spectrophotometrically measuring the product at lambda(max)=585 nm. A comprehensive chemometrical optimization treatment was successfully utilized for determining the proper optimum operating conditions for both the system and the chemical variables. The experimental design approach was employed and a 2(k) factorial design was run for studying the interaction effects of four factors namely, hydrochloric acid concentration, iron(II) concentration, delay time and flow rate. The super modified simplex algorithm was utilized for optimizing the three highly interacting factors which were, hydrochloric acid, iron(II), and delay time. The conditions obtained were 150 microl 0.110 mol l(-3) hydrochloric acid, 75 microl 0.328 mol l(-3) iron(II), 1200 s delay time and 40 microl s(-1) flow rate. The method was found to be suitable for the determination of Bromazepam in pharmaceutical preparations and the results obtained for the assay of the compound in proprietary drugs indicate that the method suffers no interference from excipients.     

Complexometric-spectrophotometric assay of tetracyclines in drug formulations

An accurate, rapid and very simple spectrophotometric method for the assay of tetracyclines (tetracycline.HCl, chlorotetracycline.HCl, demeclocycline, oxytetracycline.HCl and doxycycline) has been developed. The method is based on the complexation of iron(III) with tetracyclines in 0.001M sulphuric acid. It has been successfully applied to the assay of tetracyclines in drug formulations, and the interferences of excipients have been examined. The results have been statistically compared with those obtained by two standard methods and found to be very satisfactory.     

Chemiluminescence method for the assay of perphenazine in drug formulation using permanganate in sulphuric acid with flow injection technique and a chemometrical optimization approach

An accurate selective flow injection chemiluminescence (CL) method for the assay of perphenazine was explored. In the method 394 ppm permanganate solution was used as a chemiluminogenic reagent in 0.289 mol dm⁻³ sulphuric acid media. A photomultiplier tube was used as a detector at a total flow rate of 4.94 ml/min. Perphenazine was determined by a linear calibration plot of the following equation in the range 50–350 ppm: mV=−4.488+0.1162C, with a correlation coefficient of 0.9989 for five measurements and a relative standard deviation less than 2.33. A sampling frequency not less than 110 samples h⁻¹ was established. Three factors namely, the flow rate, sulphuric acid and permanganate concentrations were found to have an influence on the amount of chemiluminescence intensity produced. Therefore, their interaction effects were thoroughly investigated by employing the 2³ factorial design chemometrical approach and the results obtained revealed a higher interaction between sulphuric acid and permanganate and a less significant interaction for both reagents with the flow rate. The interaction of variables observed necessitated the conduct of the super modified simplex optimization procedure which has resulted in offering the proper optimum conditions as stated above and led to the quantitative assay of perphenazine. An interference study indicated that the method was suitable for application in pharmaceutical preparations.     

Design,synthesis, photophysical,and electrochemical properties of DCM‐based conjugated polymers for light‐emitting devices

A series of conjugated hyperbranched polymers, hyperbranched copolymers, and linear polymers containing 2‐pyran‐4‐ylidenemalononitrile (acceptor) and triphenylamine/fluorene (donor) units were synthesized and characterized by FTIR, ¹H NMR, thermogravimetric analyses, differential scanning calorimetry, gel permeation chromatography, UV–visible, photoluminescence, and cyclic voltammetry measurements. All the polymers show red‐light emission in the range of 566–656 nm both in solution and in solid state. The quantum efficiency of the polymers was in the range of 56–82%. Among the six polymers synthesized, only polymers containing fluorene units show T_g and polymers based on triphenylamine not exhibit T_g. The band gap of these polymers were found to be reasonably low; hyperbranched copolymer containing fluorene unit shows lowest band gap of 2.18 eV due to the stabilization of LUMO energy level by the electron withdrawing ? CN groups. The thermal and solubility behavior of the polymers were found to be good. All the EL spectra of the devices (indium‐tin oxide/poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate)/polymer/2,9‐dimethyl‐4,7‐diphenyl‐1,10‐phenanthroline/tris(8‐hydroxyquinoline)aluminum)/LiF/Al) show red‐light emission, and the device fabricated with P3 and P4 shows maximum luminance and luminous efficiency of 4104 cd m^?2 and 0.55 cd Å^?1 and 3696 cd m^?2 and 0.47 cd Å^?1, respectively, indicates that they had the best carrier balance. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Electron Impact Mass Spectra of Phenol Blocked Isocyanates

Abstract

The electron impact mass spectra of a series of substituted phenol blocked toluene diisocyanate crosslinkers were analyzed and a suitable dissociative pathway proposed.     

A parametric study of CaCO3 scaling in AISI 316 stainless steel tubes

 The formation of undesirable layer of deposits on the heat-transfer surface is defined as fouling. These deposits present a major problem in the operation and maintenance of heat exchangers, particularly in cooling-water systems. It has been generally observed that the deposits in such systems consist mainly of calcium carbonate (CaCO₃), which has inverse solubility characteristics. An experimental study was carried out to determine the effect of tube surface temperature, Reynolds number, tube diameter and salt concentration on the growth of CaCO₃ scale. In this paper, effects of some of these parameters on fouling growth are discussed. The effect of CaCO₃ concentration on the scale growth is compared with the ionic diffusion model presented by Hasson. The variation of the fouling thickness along the length of the heat exchanger is also illustrated. Furthermore, dimensionless parameters are introduced to present the fouling resistance data collected during the experimental study. Received on 14 June 2000