A Schiff base expanded porphyrin macrocycle that acts as a versatile binucleating ligand for late first-row transition metals

The coordination chemistry of the Schiff base polypyrrolic octaaza macrocycle 1 toward late first-row transition metals was investigated. Binuclear complexes with the divalent cations Ni(II), Cu(II), and Zn(II) and with the monovalent cation Cu(I) were prepared and characterized. Air oxidation of the Cu(I) ions in the latter complex to their divalent oxidation state resulted in a change in the coordination mode relative to the macrocycle.     

Design,synthesis and characterization of peptidyl boronate analogues as effective antimicrobial agents

Research on Chemical Intermediates - Antibiotic-resistant penicillin binding protein (PBPs) production is one of the reasons why bacteria develop resistance to β-lactam antibiotics, and this...     

A Convenient One-Step Synthesis of 5-(α-alkanonyl) and 5-(α-Cyclanonyl)-4-Pentanolides

The thermolysis of t-butyl perpent-4-enoate in ketones leads to the formation of 5-(α-alkanonyl) and 5-(α-cyclanonyl)-4-pentanolides with fairly good yields.     

Convenient synthesis of substituted benzo[e][1,2,4]- or [d][1,2,6]oxadiazepines,benzo[f][1,3,5]triazocines from N-aryliminoesters

We report herein a short and efficient synthesis of benz[e][1,2,4]- or [d][1,2,6]oxadiazepines and benzo[f][1,3,5]triazocines from easily prepared N-aryl iminoesters. The strategy involves a bis-nucleophile reagent (hydroxylamine or guanidine) that promotes a one-step ring closure from the starting functionalized iminoesters.     

Synthesis of substituted 1-trifluoromethyl and 1-perfluoroalkyl-3-(arylamino)prop-2-en-1-one: advances in the mechanism of Combes 2-trifluoromethyl and 2-perfluoroalkyl quinolines synthesis

We report a new synthesis and our study of the mechanism of formation of substituted 1-trifluoromethyl and 1-perfluoroalkyl-3-(phenylamino)prop-2-en-1-one starting from 3-(R-phenoxy)-3-perfluoroalkyl-prop-2-enals and arylamines. Reactivity study of the intermediates confirmed that 3-perfluoroalkyl-N,N′-diphenyl-1,5-diazapentadienes are the synthetic intermediates of the synthesis of 2-perfluoroalkylquinolines. The mechanism of the reaction of 1-trifluoromethyl and 1-perfluoroalkyl-3-(phenylamino)prop-2-en-1-one with POCl₃ was studied. To our knowledge this is the first detection and isolation of N,N′-diaryldiazapentadiene derivatives as intermediates in the Combes F-alkyl substituted quinoline synthesis starting from enaminoketones. Finally, we succeeded isolating and identifying unsymmetrically substituted 2-perfluorolakyldiazapentadiene.     

Pore-Scale Monitoring of Wettability Alteration by Silica Nanoparticles During Polymer Flooding to Heavy Oil in a Five-Spot Glass Micromodel

It is well known that the oil recovery is affected by wettability of porous medium; however, the role of nanoparticles on wettability alteration of medium surfaces has remained a topic of debate in the literature. Furthermore, there is a little information of the way dispersed silica nanoparticles affect the oil recovery efficiency during polymer flooding, especially, when heavy oil is used. In this study, a series of injection experiments were performed in a five-spot glass micromodel after saturation with the heavy oil. Polyacrylamide solution and dispersed silica nanoparticles in polyacrylamide (DSNP) solution were used as injected fluids. The oil recovery as well as fluid distribution in the pores and throats was measured with analysis of continuously provided pictures during the experiments. Sessile drop method was used for measuring the contact angles of the glass surface at different states of wettability after coating by heavy oil, distilled water, dispersed silica nanoparticles in water (DSNW), polyacrylamide solution, and DSNP solution. The results showed that the silica nanoparticles caused enhanced oil recovery during polymer flooding by a factor of 10%. The distribution of DSNP solution during flooding tests in pores and throats showed strong water-wetting of the medium after flooding with this solution. The results of sessile drop experiments showed that coating with heavy oil, could make an oil-wet surface. Coating with distilled water and polymer solution could partially alter the wettability of surface to water-wet and coating with DSNW and DSNP could make a strongly water-wet surface.     

Sub- and superluminal propagation of intense pulses in media with saturated and reverse absorption

We develop models for the propagation of intense pulses in solid state media which can have either saturated absorption or reverse absorption. We model subluminal propagation in ruby and superluminal propagation in alexandrite as three and four level systems, respectively, coupled to Maxwell's equations. We present results well beyond the traditional pump-probe approach and explain the experiments of Bigelow et al. [Phys. Rev. Lett. 90, 113903 (2003)]Science 301, 200 (2003)]] on solid state materials.     

Syntheses,characterization, X-ray crystal structures and emission properties of copper(II), zinc(II) and cadmium(II) complexes of pyridyl–pyrazole derived Schiff base ligand – Metal selective ligand binding modes

The varying coordination modes of the title ligand, L [5-methyl-1-(pyridin-2-yl)-N′-[pyridin-2-ylmethylidene]pyrazole-3-carbohydrazide] towards the different metal centers is reported by preparation and characterization of Cu(II), Zn(II) and Cd(II) complexes, [Cu(L)NO₃.H₂O](NO₃) (1) [Zn(L)₂](ClO₄)₂·2DMF (2) and [Cd(L)(I)₂] (3) respectively. In 1, the neutral ligand serves as tetradentate 4 N donor where both pyridine and pyrazole nitrogen atoms of pyridyl–pyrazole part are coordinatively active, leaving the carbonyl oxygen of the carbohydrazide part inactive. The same pyridine and pyrazole N atoms remain abstained from the coordination process towards the Zn(II) and Cd(II) metal centers. For 2 and 3 the ligand behaves as a tridentate NNO donor where the two nitrogen atoms come from azomethine, pyridine of pyridine-2-carbaldehyde parts and O from carbonyl oxygen atoms (carbohydrazide part). The complex 1 and 2 are distorted octahedral while complex 3 adopts distorted square pyramidal geometry. All the complexes are X-ray crystallographically characterized.     

Study of Microscopic and Macroscopic Displacement Behaviors of Polymer Solution in Water-Wet and Oil-Wet Media

Performance of a polymer flood process requires the knowledge of rheological behavior of the polymer solution and reservoir properties such as rock wettability. To provide a better understanding of effects of polymer chemistry and wettability on the performance of a polymer flood process, a comprehensive experimental study was conducted using a two-dimensional glass micromodel. A series of water and polymer flood processes were carried out at different polymer molecular weights, degrees of polymer hydrolysis, and polymer concentrations in both water-wet and oil-wet systems. Image processing technique was applied to analyze and compare microscopic and macroscopic displacement behaviors of polymer solution in each experiment. From micro-scale observations, the configuration of connate water film, polymer solution trapping, flow of continuous and discontinuous strings of polymer solution, piston-type displacement of oil, snap-off of polymer solution, distorted flow of polymer solution, emulsion formation, and microscopic pore-to-pore sweep of oil phase were observed and analyzed in the strongly oil-wet and water-wet media. Rheological experiments showed that a higher polymer molecular weight, degree of hydrolysis, and concentration result in a higher apparent viscosity for polymer solution and lower oil–polymer viscosity ratio. It is also shown that these parameters have different impacts on the oil recovery in different wettabilities. Moreover, a water-wet medium generally had higher recovery in contrast with an oil-wet medium. This experimental study illustrates the successful application of glass micromodel techniques for studying enhanced oil recovery (EOR) processes in five-spot pattern and provides a useful reference for understanding the displacement behaviors in a typical polymer flood process.     

A Catalyst and Solvent Free Route for the Synthesis of N-Substituted Pyrrolidones from Levulinic Acid

An efficient, metal-free, catalyst-free and solvent-free methodology for the reductive amination of levulinic acid with different anilines has been developed using HBpin as the reducing reagent. This protocol offers an excellent method to avoid solvents and added catalysts on the synthesis of different kinds of N-substituted pyrrolidones under metal free conditions. It is also the first report for the synthesis of different pyrrolidones by solvent-free as well as catalyst-free methods. The proposed mechanism for the formation of pyrrolidone has been supported by DFT calculations and control experiments.