One-pot synthesis of multicomponent pyrazole-4-carbonitrile derivatives under solvent-free condition by using engineered polyvinyl alcohol catalyst

Heterocyclic chemistry has fascinated the researchers owing to its wide range of applications in various chemical fields. With this perspective, herein we present an environmentally benign procedure for the synthesis of pyrazole and its derivatives through multicomponent reaction by using SPVA as a heterogeneous acid catalyst. The synthesis protocol of SPVA catalyst includes functionalization of polyvinyl alcohol by sulfonic acid groups. The synthesized SPVA catalyst was then subjected to several characterization techniques to confirm its formation and study its physicochemical properties. The SPVA catalyst was then tested for its activity toward a multicomponent reaction of aromatic aldehyde, malononitrile and phenyl hydrazine. The SPVA catalyst with sufficient acidic sites displayed appreciable catalytic performance yielding 89% of the desired pyrazole product under ambient reaction conditions. The SPVA catalyst showed recyclability up to the sixth cycle without considerable loss in its activity. Furthermore, we made an effort to demonstrate the plausible mechanistic pathway for the SPVA-catalyzed pyrazole synthesis reaction. Interestingly, the present synthetic approach could effectively produce pyrazole products with high yields in the absence of base and solvent and in short reaction time making it a green and sustainable process.

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A columnar phase of dendritic lipid-based cationic liposome-DNA complexes for gene delivery: hexagonally ordered cylindrical micelles embedded in a DNA honeycomb lattice

Gene therapy holds great promise as a future approach to fighting disease and is explored in worldwide clinical trials. Cationic liposome (CL)-DNA complexes are a prevalent nonviral delivery vector, but their efficiency requires improvement and the understanding of their mechanism of action is incomplete. As part of our effort to investigate the structure-transfection efficiency relationships of self-assembled CL-DNA vectors, we have synthesized a new, highly charged (16+) multivalent cationic lipid, MVLBG2, with a dendritic headgroup. Our synthetic scheme allows facile variation of the headgroup charge and the spacer connecting hydrophobic and headgroup moieties as well as gram-scale synthesis. Complexes of DNA with mixtures of MVLBG2 and neutral 1,2-dioleoyl-sn-glycerophosphatidylcholine (DOPC) exhibit the well-known lamellar phase at 90 mol % DOPC. Starting at 20 mol % dendritic lipid, however, two novel nonlamellar phases are observed by synchrotron X-ray diffraction. The structure of one of these phases, present in a narrow range of composition around 25 mol % MVLBG2, has been solved. In this novel dual lattice structure, termed H(I)C, hexagonally arranged tubular lipid micelles are surrounded by DNA rods forming a three-dimensionally continuous substructure with honeycomb symmetry. Complexes in the H(I)C phase efficiently transfect mouse and human cells in culture. Their transfection efficiency, as well as that of the lamellar complexes containing only 10 mol% dendritic lipid, reaches and surpasses that of commercially available, optimized DOTAP-based complexes. In particular, complexes containing MVLBG2 are significantly more transfectant over the entire composition range in mouse embryonic fibroblasts, a cell line empirically known to be hard to transfect.     

Improving performance of FxRLS algorithm for active noise control of impulsive noise

Active noise control (ANC) systems employing adaptive filters suffer from stability issues in the presence of impulsive noise. New impulsive noise control algorithms based on filtered-x recursive least square (FxRLS) algorithm are presented. The FxRLS algorithm gives better convergence than the filtered-x least mean square (FxLMS) algorithm and its variants but lacks robustness in the presence of high impulsive noise. In order to improve the robustness of FxRLS algorithm for ANC of impulsive noise, two modifications are suggested. First proposed modification clips the reference and error signals while, the second modification incorporates energy of the error signal in the gain of FxRLS (MGFxRLS) algorithm. The results demonstrate improved stability and robustness of proposed modifications in the FxRLS algorithm. However, another limitation associated with the FxRLS algorithm is its computationally complex nature. In order to reduce the computational load, a hybrid algorithm based on proposed MGFxRLS and normalized step size FxLMS (NSS-FXLMS) is also developed in this paper. The proposed hybrid algorithm combines the stability of NSS-FxLMS algorithm with the fast convergence speed of the proposed MGFxRLS algorithm. The results of the proposed hybrid algorithm prove that its convergence speed is faster than that of NSS-FxLMS algorithm with computational complexity lesser than that of FxRLS algorithm.     

Effect of miscibility and interaction on the properties of polymethylmethacrylate/aramid nanoblends

The generation of supramolecularly organized structures from intermolecular interaction motivated us to fabricate new miscible nanoblends of polymethylmethacrylate (PMMA) and aramid. The polyamide, prepared through the condensation of 1,5‐diaminonaphthalene and 1,4‐phenylenediamine with isopthaloyl chloride, was incorporated into PMMA matrix to produce completely miscible nanostructured blends via physical interlocking. The influence of polymer–polymer interaction on the macroscopic properties of blends were studied using mechanical testing, thermogravimetric analysis, differential scanning calorimetry, and scanning electron microscopy. Ample adhesion between the blend components revealed higher tensile strength in the range 51–58 MPa. The physical interaction of PMMA with varying aramid content altered blend morphology significantly, i.e. from ellipsoidal to circular realms having well‐defined boundaries and knitted nanofibril network. Blends with 10–70 wt% aramid, thus, possessed exclusive patterns owing to nanolevel compatibility between two phases. Differential scanning calorimetry results also designated exclusively miscible blends with glass transition between 67–81°C, lower than that of pristine polymers. Ten percent gravimetric loss temperature (T₁₀) increased from 465°C to 531°C with increasing aramid content from 10 to 70 wt%. Novel nanoblends holding spherical/cylindrical supramolecular arrangement, easy processing, and thermal and mechanical integrity can be potentially favorable in many industrial applications. Copyright © 2013 John Wiley & Sons, Ltd.     

Synthetic approaches toward piperidine related structures: A review

Abstract

The current review covers explosive development of various synthetic approaches for piperidine scaffold and its analogues in the last few decades. The piperidine ring system is a key motif in many natural alkaloids and synthetic organic compounds. Further, piperidine moiety has gained significant consideration in drug discovery due to its wide range of therapeutic applications.     

Novel Synthesis of 2-(2-(3-Hydroxy-5-oxo-4-phenylthiophen-2(5H)-ylidene)-2-phenylacetamido)propanoic Acid Analogues and Their Anti-Inflammatory Properties

This article describes the reaction of 3,6-diphenyl-thieno[3,2-b]furan-2,5-dione 1 with different amino acids 2a–j in glacial acetic acid which afforded the 2-(2-(3-hydroxy-5-oxo-4-phenylthiophen-2(5H)-ylidene)-2-phenylacetamido)propanoic acid analogues 3a–j and also describes the reaction of 3,6-diphenyl-thieno[3,2-b]thiophene-2,5-dione 4 with different amino acids 5a–e in acidic medium to give 2-(2-(3-mercapto-5-oxo-4-phenylthiophen-2(5H)-ylidene)-2-phenylacetamido)propanoic acid analogues 6a–e. All the compounds have been screened for their anti-inflammatory activity against the carrageenan induced rat paw edema in albino rats. In the primary screening, some of the compounds exhibited appreciable activity.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Catalyst free synthesis of mono- and disubstituted pyrimidines from O-acyl oximes

Transition-metal or iodine catalyzed transformations of O-acyl oximes to various N-heterocycles are well established. Herein, we report a catalyst free, oxime carboxylate based, three-component condensation method to access mono- and disubstituted pyrimidines. A broad range of substituted pyrimidines were prepared in moderate to excellent yields. Control experiments reveal that in situ generated formamidine is the key intermediate.     

Reactions of Unsaturated Quinoline Triosmium Clusters [Os3(CO)9(μ3-η2-C9H5(4-R)N)(μ-H)] (R=Me or H) with Tetramethylthiourea: X-ray Structures of [Os3(CO)8(μ-η2-C9H5(4-Me)N)(η2-SC(NMe2NCH2Me)(μ-H)2] and [Os3(CO)9(μ-η2-C9H6N)(η1-SC(NMe2)2)(μ-H)]

Treatment of the electronically unsaturated 4-methylquinoline triosmium cluster $[\hbox{Os}_{3}\hbox{(CO)}_{9}(\upmu_3\hbox{-}\upeta^{2}\hbox{-}\hbox{C}_{9}\hbox{H}_{5} \hbox{(4-Me)N})(\upmu\hbox{-H})]$ (1) with tetramethylthiourea in refluxing cyclohexane at 81°C gave $[\hbox{Os}_{3}\hbox{(CO)}_{8}(\upmu\hbox{-}\upeta^{2}\hbox{-C}_{9}\hbox{H}_{5} \hbox{(4-Me)N})(\upeta^2\hbox{-SC}(\hbox{NMe}_2\hbox{NCH}_2\hbox{Me})(\upmu \hbox{-H})_2]$ (2) and $[\hbox{Os}_{3}\hbox{(CO)}_{9}(\upmu\hbox{-}\upeta^{2}\hbox{-C}_{9}\hbox{H}_{5}\hbox{(4-Me)N})(\upeta^1\hbox{-SC}(\hbox{NMe}_2)_2)(\upmu\hbox{-H})]$ (3). In contrast, a similar reaction of the corresponding quinoline compound $[\hbox{Os}_{3}\hbox{(CO)}_{9}(\upmu_{3}\hbox{-}\upeta^{2}\hbox{-C}_{9}\hbox{H}_{6}\hbox{N})(\upmu\hbox{-H})]$ (4) with tetramethylthiourea afforded $[\hbox{Os}_{3}\hbox{(CO)}_{9}(\upmu\hbox{-}\upeta^{2}\hbox{-C}_{9}\hbox{H}_{6}\hbox{N})(\upeta^{1}\hbox{-SC(NMe}_{2})_{2})(\upmu\hbox{-H)}]$ (5) as the only product. Compound 2 contains a cyclometallated tetramethylthiourea ligand which is chelating at the rear osmium atom and a quinolyl ligand coordinated to the Os₃ triangle via the nitrogen lone pair and the C(8) atom of the carbocyclic ring. In 3 and 5, the tetramethylthiourea ligand is coordinated at an equatorial site of the osmium atom, which is also bound to the carbon atom of the quinolyl ligand. Compounds 3 and 5 react with PPh₃ at room temperature to give the previously reported phosphine substituted products $[\hbox{Os}_{3}\hbox{(CO)}_{9}(\upmu \hbox{-}\upeta^{2}\hbox{-C}_{9}\hbox{H}_{5}\hbox{(4-Me)N)(PPh}_{3})(\upmu\hbox{-H)}]$ (6) and $[\hbox{Os}_{3}\hbox{(CO}_{9}(\upmu \hbox{-}\upeta^{2}\hbox{-C}_{9}\hbox{H}_{6}\hbox{N)(PPh}_{3})(\upmu\hbox{-H)}]$ (7) by the displacement of the tetramethylthiourea ligand.     

Mixed matrix membranes of polysulfone/polyimide reinforced with modified zeolite based filler: Preparation,properties and application

In this work,polysulfone/polyimide (PSf/PI) mixed matrix membranes were fabricated by reinforcement of modified zeolite (MZ) particles through solution casting method for investigation of antibacterial activity against two gram negative bacteria (Salmonella typhi,Klebsellapneumonia) and two gram positive bacteria (Staphylococcus aureus,Bacillus subtilis).The modified zeolite particles were incorporated to PSf and PI matrix and the influence of these particles on thermal,mechanical and structural properties was evaluated.The morphological evolution was investigated through scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analysis,which revealed good compatibility between organic polymer matrix and inorganic filler.Mechanical stability was investigated by tensile testing while thermal analysis was evaluated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC).This revealed improvement in thermal properties with increasing filler concentration from 1 wt％ to 10 wt％.Structural analysis was successfully done using X-ray diffraction analysis (XRD) and Fourier transform infrared (FTIR) spectroscopy.Solvent content of fabricated mixed matrix membranes was observed to decrease while moving from more hydrophilic to less hydrophilic solvent.However,addition of filler content enhanced the porosity of fabricated membranes.The synthesized mixed matrix membranes exhibited good antibacterial activity and the highest activity was shown by PSf/PI/MZ mixed matrix membrane.Therefore,the combination effect of PSf,PI and MZ sufficiently enhanced the antibacterial activity of mixed matrix membranes.