Organosoluble and thermally stable polyimides derived from a new diamine containing bulky-flexible triaryl pyridine pendent group

A novel kind of aromatic diamine,N-(4-(4-(2,6-diphenyl pyridine-4-yl)phenoxy)phenyl)-3,5-diaminobezamide (DPDAB),was synthesized via aromatic nucleophilic substitution of 3,5-dinitrobenzoylchloride with 4-(4-(2,6- diphenylpyridine-4-yl)phenoxy)aniline(DPPA),followed by palladium-catalyzed hydrazine reduction.This monomer was used to prepare polyimides(PIs)based on reaction with several commerically avaiable tetracarboxylic dianhydrides such as pyromellatic dianhydride(PMDA),benzophenone tetracarboxylic acide dianhydride(BTDA)and bicycle[2.2.2]oct-7-enc- 2,3,5,6-tetracarboxylic dianhydride(BCDA).These PIs had inherent viscosity in the range of 0.34-0.76 dL/g and showed good solubility in various aprotic polar solvents.The glass-transition tempratures(T_gs)of the PIs were in the range of 184-302℃,and showed high thermal stability with 10%weight loss in the temperature range of 360-500℃under nitrogen atmosphere.     

Crystallization kinetics and optical band gap studies of Se96In4 glass before and after slow neutron irradiation

Results of differential scanning calorimetry (DSC) under non-isothermal condition on Se₉₆In₄ semiconducting chalcogenide glass before and after slow neutron irradiation, for different exposure times, have been reported and discussed. Some of Sn atoms have been injected into the glass by nuclear transmutation processes and the binary glass is converted into a ternary. This is accompanied by an increase in the activation energy of crystallization, E_c, and in the glass transition temperature, T_g and a decrease in the glass transition activation energy, E_t, in the onset crystallization temperature, T_c and in the peak temperature of crystallization T_p. Optical band gap measurements have also been carried out, before and after irradiation, on identical thin pellets of Se₉₆In₄ glass. The energy band gap, E_g, is found to decrease upon irradiation. These effects have been attributed to a structural change upon doping and to irradiation induced defects.     

Extending Time Profile of Morphine‐Induced Analgesia Using a Chitosan‐Based Molecular Imprinted Polymer Nanogel

Chitosan‐based molecular imprinted polymer (CS‐MIP) nanogel is prepared in the presence of morphine template, fully characterized and used as a new vehicle to extend duration of morphine analgesic effect in Naval Medical Research Institute mice. The CS‐MIP nanogel with ≈25 nm size range exhibits 98% loading efficiency, and in vitro release studies show an initial burst followed by an extended slow release of morphine. In order to study the feasibility of CS‐MIP nanogel as morphine carrier, 20 mice are divided into two groups randomly and received subcutaneous injection of morphine‐loaded CS‐MIP and morphine (10 mg kg^?1) dissolved in physiologic saline. Those received injection of morphine‐loaded CS‐MIP show slower and long lasting release of morphine with 193 min effective time of 50% (ET50) analgesia compared to 120 min ET50 in mice received morphine dissolved in physiologic saline. These results suggest that CS‐MIP nanogel can be a possible strategy as morphine carrier for controlled release and extension of its analgesic efficacy.

     

Microemulsions of Potassium Oleate,Tween-20, Propylene Carbonate,and Ethylene Glycol as Drug Vehicles for Mefenamic Acid

Different microemulsions were prepared with and without mefenamic acid (MFA). The base microemulsion was mainly composed of distilled water; the aqueous phase, propylene carbonate; the oil phase, potassium oleate; the surfactant, and finally di-ethylene glycol; the cosurfactant. The effect of mixing ionic (potassium oleate) with nonionic (Tween-20) surfactant was investigated via constructing the phase diagrams of such systems. Changes in conductivity and viscosity of the freshly prepared microemulsion over time were monitored as an indication for the stability of the microemulsion. Measurements were carried out at room temperature, after a freeze-thaw cycle and also after storage for 3 days at 60°C, where the latter is treated as an accelerated test for the time-temperature effects on the stability of a microemulsion. It was found that a set of surfactants, instead of a single surfactant, and inclusion of cosurfactant resulted in a broader region where a stable microemulsion is predominant. At a mass ratio of 1:2 of potassium oleate to Tween-20, O/W microemulsions were found to have maximum stability among all examined systems, under the accelerated test, such that they have a minimum portion of combined surfactants and cosurfactant of 60 wt% and maximum of 80 wt%. With the aforementioned specifications, no phase separation and neither significant change in the conductivity nor in the viscosity was observed in any of the examined systems after subjecting them both to the accelerated and freeze-thaw cycle test, indicating that such systems were thermodynamically stable. Samples of micro emulsions passing previous tests were further subjected to an acidic medium by dispersing 1 g of MFA-containing microemulsion in 10 g HCl solution (pH 1) in a shaking water bath at 37°C, for a 6 hour period. The maximum solubility of MFA in a stable microemulsion was approximately 5 wt%, evaluated at room temperature.     

Ultrasound assisted dehydrogenation of 2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxamides

Dehydrogenation of various 2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxamides (THPMs) to 2-oxo-1,2-dihydropyrimidine-5-carboxamides (DHPMs) using tetrabutylammonium peroxydisulfate (TBAPS) as an efficient oxidizing agent under thermal and sono-thermal conditions has been investigated. In contrast to the thermal reaction, a decrease of the amount of oxidant and an increase of the rate of reaction are observed by simultaneously applying heat and ultrasound. The nature of both C-4 and C-5 substituents on the heterocyclic ring influences the rate of reaction under both conditions. The proposed electron-transfer-induced dehydrogenation in this study is supported by conductometric studies.     

Cytochrome c embraced in sodium dodecyl sulfate nano-micelle as a homogeneous nanostructured peroxidase

A homogeneous nanostructured enzyme (artificial peroxidase, AP) with suitable catalytic efficiency was generated using bovine heart cytochrome c (Cyt c) and sodium dodecyl sulfate nano-micelles in 50?mM phosphate buffer pH 10.5 at 25?°C. The Michaelis?CMenten (K _m) and catalytic rate (k _cat) of the AP were determined to be 21.6?±?1.2???M and 0.474?±?0.013?s^?1, respectively. The catalytic efficiency of the AP was 0.0219?±?0.002???M^?1s^?1, which was 30?±?1.5?% as efficient as the native horseradish peroxidase (HRP). The mean diameter of AP was measured to be 6.4?nm using dynamic light scattering technique. The UV?CVis spectrometry, circular dichroism, surface tension, isothermal titration calorimetric and electrochemistry methods were utilized for additional characterization of the AP. Together our results suggest that the AP generated here can be used in place of HRP in industrial and commercial fields under some extreme conditions.     

Synthesis and characterization of Schiff-base-containing polyamides

A series of new Schiff base polyamides（PAs） were synthesized by polycondensation of benzilbisthiosemicarbazone diamine（LH₆） with different commercially available aliphatic and aromatic diacid chlorides. The monomer and all the PAs were characterized by FTIR,¹H-NMR,and elemental analysis.The prepared polyamides showed inherent viscosities in the range of 0.30-0.36 dL/g in DMF at 25℃,indicating their moderate molecular weight.The PAs were completely soluble in aprotic polar solvents such as dimethylformamide（DMF）,N-methylpyrolidone（NMP）, tetrachloroethane（TCE）,dimthylsulfoxide（DMSO） and also in H₂SO₄ and partially soluble in THF,acetone and chloroform at room temperature.Thermal analysis showed that these PAs were practically amorphous and exhibited 10%weight loss above 220℃.     

Synthesis of New Furo[2,3‐d]pyrimidines and Pyrimido[4′,5′:4,5]furo[2,3‐d]pyrimidines

Sodium salt of 4‐hydroxy‐6‐methyl‐2‐phenylpyrimidine‐5‐carbonitrile ( 3 ) was subjected to alkylation with different a‐halo compounds, where the corresponding O‐alkylated products 4_a‐g were obtained. Ring closure of the O‐alkylated product 4_a‐c performed using sodium ethoxide in refluxing ethanol afforded furo[2,3‐d]pyrimidines 5_a‐c The latter compounds on reaction with a variety of reagents gave other new furopyrimidines as well as a number of furodipyrimidines.     

Study Kinetics of Thermal Decomposition and Electrochemical Oxidation by Using Nanocomposite Paste of Novel Poly(amide-ether)s Derived from Asymmetric Diamine

A new asymmetric diamine containing diarylimodazole pendant was synthesized from the nucleophilic substitution reaction of 1-fluoro-4-nitrobenzene and 2,4-dihydroxy benzaldehyde in the presence of K₂CO₃, followed by reaction with benzil and ammonium acetate for the preparation of imidazole ring. This novel diamine was used to prepare poly(amide-ether) (PAE) in reaction with different commercially available dicarboxylic acids via direct polycondensation using triphenyl phosphite and pyridine (Py) as catalyst. The PAEs were fully characterized and their properties such as inherent viscosity, solubility, optical, thermal and kinetics of thermal decomposition, and electrochemical oxidation were investigated. The polymers had inherent viscosity in the range of 0.47–0.65 dL/g and were noncrystalline with excellent solubility in various polar aprotic organic solvents. Their T_g values ranged from 200 to 355°C and 10% weight loss temperature above 450°C in nitrogen and left more than 70% residue at 650°C. The kinetic parameters of thermal degradation such as activation energy, entropy, enthalpy and Gibbs free energy of thermal decomposition have been evaluated using different equations. We also report electrochemical oxidation of the resulting polymers in aqueous solution by using cyclic voltammetry technique on the multi-walled carbon nanotube-modified glassy carbon electrode.     

Optical properties of a-Se90In10−x Snx chalcogenide thin films before and after gamma irradiation

Amorphous Se₉₀In_10?xSn_x (x=2, 4, 6, and 8) thin films of thickness 1000 Å were prepared on glass substrates by the thermal evaporation technique. Optical parameters of the films were investigated, in the wavelength range 400–700 nm, before and after irradiation by 4, 8, and 12 kGy doses of γ-ray. The optical absorption coefficient α for as-deposited and gamma irradiated films was calculated from the reflectance R and transmittance T measurements, which were recorded at room temperature. From the knowledge of α, at different wavelengths, the optical band gap E_g was calculated for all compositions of Se–In–Sn thin films before and after gamma irradiation. Results indicate that allowed indirect optical transition is predominated in as-deposited and irradiated films. Besides, it is found that the band gap decreases with increasing Sn concentration and this is attributed to the corresponding decrease in the average single bond energy of the films. The band gap, after irradiation at different doses of γ-ray, was found to decrease for all compositions of the studied films. This post-irradiation decrease in the band gap was interpreted in terms of a bond distribution model.