Synthesis of a New Class of Highly Functionalized Phosphorus Ylides Containing Heterocyclic Compounds

The zwitterionic intermediate generated from the reaction of triphenylphosphine with electron deficient acetylenic compounds was trapped by various NH acids. The synthesis resulted in a new class of highly functionalized heterocyclic compounds. Some of the reactions produced E and Z isomers. And the stability and transformation of them were studied by dynamic ¹H NMR and density functional theory (DFT) calculations.     

Stereoselective synthesis of functionalised carbocyclic amides: construction of the syn-(4aS,10bS)-phenanthridone skeleton

A new synthetic approach has been developed for the preparation of 7-deoxypancratistatin analogues bearing a syn-(4aS,10bS)-phenanthridone ring junction. A one-pot tandem process involving a substrate-directed Overman rearrangement and ring closing metathesis reaction was developed for the stereoselective synthesis of a carbocyclic allylic trichloroacetamide. Conversion to a 6-bromopiperonyl amide, followed by a Heck reaction generated a homoallylic alcohol and completed the syn-(4aS,10bS)-phenanthridone carbon skeleton. Stereoselective epoxidation and dihydroxylation of the syn-(4aS,10bS)-phenanthridone framework was then investigated leading to the preparation of new analogues of 7-deoxypancratistatin.     

EPR Study of γ-Irradiated UHMWPE Doped with Vitamin E: Assessment of Thermal Effects on the Organic Radicals During Vitamin E Diffusion

Thermal effects on ultra-high-molecular-weight polyethylene (UHMWPE) residual radicals during the vitamin E diffusion process were studied in detail. Electron paramagnetic resonance (EPR) technique showed a significant reduction in concentrations of radiation-induced primary (alkyl (–CH₂– ^?CH–CH₂–), allyl (–CH₂–^?CH=CH–CH–CH₂–) and polyenyl (–^?CH–[CH=CH–] _m –) with m > 3) radicals for both control and vitamin E-doped samples. The concentrations of radiation-induced primary radicals (RIPRs) were found to decrease proportionally with the heat/diffusion time. While the EPR spectra of the control samples showed only polyethylene (PE) radicals, the spectra of vitamin E-doped samples were found to exhibit vitamin E radicals in addition to PE radicals. Of particular interest, the heat involved during vitamin E diffusion plays a significant role in reducing the radiation-induced primary radicals of UHMWPE. For 120 min of heat/diffusion time, the available quantity of primary radicals in control samples were found to be ~7.5 % of initial radicals. The leftover amounts of these primary radicals for vitamin E-doped samples were approximately ~10.0 %. In addition to this, EPR power saturation techniques were also used to assess the effects of initial heat/diffusion treatment on the oxygen-induced residual radicals (OIRRs): R₁ (–^?CH–[CH=CH–] _m –) with m > 3 and R₂ (^?OCH–[CH=CH–] _m –) with m = 2 or 3. It was found that the concentration of OIRRs also decreases proportionally with initial heat/diffusion time. The remaining amount of OIRRs relative to leftover RIPRs after heat/diffusion was found to be approximately 4.0 % in controls and was still found to be 10.0 % in vitamin E-doped UHMWPE. This may indicate that vitamin E slows down the oxidation processes, which may contribute to the strong oxidation resistance of vitamin E-doped UHMWPE.     

An efficient scheme for digital watermarking using chaotic map

This paper presents the new digital watermarking algorithm based on the chaotic map. Data can easily be hidden in images by using the least significant bits. In the anticipated algorithm, the logistic map is employed for locating embedding positions of chaotic watermark generation and a novel watermarking scheme is proposed. Simulation results reveal that the proposed technique is feasible and watermarks are indiscernible. The results illustrate that mean of energy, correlation, contrast, and homogeneity analyses of the proposed algorithm are quite optimal.     

First-principles study of vibrational properties of TiSiO4 clusters

First-principles calculations were performed to investigate the vibrational properties of monomers and dimers of titania, silica, and titania-silica hybrid clusters. Density functional theory-based formulism was employed to optimize the geometry at the B3LYP level and calculate the infrared and Raman spectra of the clusters by using the GGA-PBE exchange-correlation functional. It was found that the vibrational spectra of Ti₂O₄, Si₂O₄, and TiSiO₄ hybrid clusters provide fingerprint information about structures and structural transitions during the formation of cluster structures. In the case of Si₂O₄ the mode at 410 cm⁻¹ exhibited the largest vibration of Si atoms, whereas in the case of Ti₂O₄ the mode at 442 cm⁻¹ exhibited the largest vibration of Ti atoms. The hybrid cluster TiSiO₄ was structured using two different methods to explore the effects of starting geometry on the structures and vibrational modes of the clusters. The structural properties of the clusters remained unchanged but vibrational modes were found to be different. It is found that Si shows notable vibrations, but the metal atom Ti merely shows any vibration in the case of TiSiO₄ hybrid clusters. The low and intermediate frequency modes were stiffened, whereas the three highest frequency modes were softened when the starting geometry of the hybrid clusters was changed from Si₂O₄ to Ti₂O₄.     

Recent progress in the synthesis of diclofenac based NSAIDs analogs/derivatives

Non-steroidal anti-inflammatory drugs (NSAIDs) are known for inhibition of cyclooxygenase-1 (COX-1) and cyclooxygenase-2 (COX-2). Diclofenac and its analogs, having phenylacetic acid moiety, are important NSAIDs. In this review article, various methodologies developed after 90?s for the synthesis of various analogs/derivatives of diclofenac sodium have been discussed and summarized.     

Copper Salt Catalyzed Synthesis of Functionalized 2H‐Pyranes

A copper‐catalyzed reaction between terminal alkynes, oxiranes, and malonitrile has been described. In this transformation, copper acetylide was attacked on oxiranes to form homopropargyl alkoxy‐copper intermediate that was further transferred to 2H‐pyrane skeletons by reaction with malonitrile. We found that the reaction was not productive without hexafluoroisopropanol.     

Catalytic performance of ZnFe2O4 nanoparticles prepared from the [ZnFe2O(CH3COO)6(H2O)3]·2H2O complex under microwave irradiation

Research on Chemical Intermediates - Using the heterometallic oxo-centered trinuclear [ZnFe2O(CH3COO)6(H2O)3]·2H2O complex as a novel precursor, pure and single-phase ZnFe2O4 nanostructure was...     

New Correlative Models to Improve Prediction of Fracture Permeability and Inertial Resistance Coefficient

Presence of fracture roughness and occurrence of nonlinear flow complicate fluid flow through rock fractures. This paper presents a qualitative and quantitative study on the effects of fracture wall surface roughness on flow behavior using direct flow simulation on artificial fractures. Previous studies have highlighted the importance of roughness on linear and nonlinear flow through rock fractures. Therefore, considering fracture roughness to propose models for the linear and nonlinear flow parameters seems to be necessary. In the current report, lattice Boltzmann method is used to numerically simulate fluid flow through different fracture realizations. Flow simulations are conducted over a wide range of pressure gradients through each fracture. It is observed that creeping flow at lower pressure gradients can be described using Darcy’s law, while transition to inertial flow occurs at higher pressure gradients. By detecting the onset of inertial flow and regression analysis on the simulation results with Forchheimer equation, inertial resistance coefficients are determined for each fracture. Fracture permeability values are also determined from Darcy flow as well. According to simulation results through different fractures, two parametric expressions are proposed for permeability and inertial resistance coefficient. The proposed models are validated using 3D numerical simulations and experimental results. The results obtained from these two proposed models are further compared with those obtained from the conventional models. The calculated average absolute relative errors and correlation coefficients indicate that the proposed models, despite their simplicity, present acceptable outcomes; the models are also more accurate compared to the available methods in the literature.