Synthesis, characterization and low temperature electrical conductivity of Polyaniline/NiFe2O4 nanocomposites

Conducting polymer/ferrite nanocomposites with an organized structure provide a new functional hybrid between organic and inorganic materials. The most popular among the conductive polymers is the polyaniline (PANI) due to its wide application in different fields. In the present work nickel ferrite (NiFe2O4) nanoparticles were prepared by sol-gel citrate-nitrate method with an average size of 21.6nm. PANI/NiFe2O4 nanoparticles were synthesized by a simple general and inexpensive in-situ polymerization in the presence of NiFe2O4 nanoparticles. The effects of NiFe2O4 nanoparticles on the dc-electrical properties of polyaniline were investigated. The structural components in the nanocomposites were identified from Fourier Transform Infrared (FTIR) spectroscopy. The crystalline phase of nanocomposites was characterized by X-Ray Diffraction (XRD). The Scanning Electron Micrograph (SEM) reveals that there was some interaction between the NiFe2O4 particles and polyaniline and the nanocomposites are composed of polycrystalline ferrite nanoparticles and PANI. The dc conductivity of polyaniline/NiFe2O4 nanocomposites have been measured as a function of temperature in the range of 80K to 300K. It is observed that the room temperature conductivity sigma(RT) decreases with increase in the relative content of NiFe2O4. The experimental data reveals that the resistivity increases for all composites with decrease of temperature exhibiting semiconductor behaviour.

A Mild Protocol for the Regioselective Ring Opening of Doubly Activated Cyclopropanes by Using Selenolates Generated in Situ: Synthesis of Functionalized Organoselenium Compounds

A variety of functionalized organoselenium compounds were synthesized from doubly activated cyclopropanes and diselenides in the presence of sodium borohydride. A range of substituents were stable under these reaction conditions. Additionally, we extended the scope of the method by reducing nitro groups in the products to give the corresponding selenium-containing unnatural amino acids.

Formal synthesis of degraded sterol (+)-aplykurodinone-1

The formal synthesis of aplykurodinone-1 is accomplished starting from a suitably functionalized bicyclic lactone having the requisite cis-fused ring junction with a quaternary chiral center that was assembled following a Cp2TiCl-mediated radical cyclization protocol. Our synthetic route further elaborates implementation of Grubbs ring closing metathesis (RCM), Eschenmoser-Claisen rearrangement and iodo-lactonization reactions for the synthesis of the final tricyclic precursor of the target molecule. (C) 2015 Elsevier Ltd. All rights reserved.

Continuous synthesis of high quality CdSe quantum dots in supercritical fluids

We demonstrate in here a powerful scalable technology to synthesize continuously high quality CdSe quantum dots (QDs) in supercritical hexane. Using a low cost, highly thermally stable Cd-precursor, cadmium deoxycholate, the continuous synthesis is performed in 400 mu m ID stainless steel capillaries resulting in CdSe QDs having sharp full-width-at-half-maxima (23 nm) and high photoluminescence quantum yields (45-55%). Transmission electron microscopy images show narrow particles sizes distribution (sigma <= 5%) with well-defined crystal lattices. Using two different synthesis temperatures (250 degrees C and 310 degrees C), it was possible to obtain zinc blende and wurtzite crystal structures of CdSe QDs, respectively. This synthetic approach allows achieving substantial production rates up to 200 mg of QDs per hour depending on the targeted size, and could be easily scaled to gram per hour.

Synthesis and characterization of magnetic and conductive nickel ferrite-polyaniline nanocomposites

Conducting polymer/ferrite nanocomposites with an organized structure provide a new functional hybrid between organic and inorganic materials. The most popular among the conductive polymers is the polyaniline due to its wide application in different fields. In the present work nickel ferrite nanoparticles were prepared by sol-gel citrate-nitrate method. Polyaniline/nickel ferrite nanocomposites were synthesized by a simple general and inexpensive in-situ polymerization in the presence of nickel ferrite nanoparticles. The effects of nickel ferrite nanoparticles on the DC-electrical and magnetic properties of polyaniline were investigated. The structural, morphological and thermal stability of nanocomposites were characterized by X-ray diffraction, FTIR, scanning electron micrograph and TGA. The DC conductivity of polyaniline/nickel ferrite nanocomposites have been measured as a function of temperature in the range of 80K to 300K. The magnetic properties of the nanocomposites were measured using vibrating sample magnetometer in the temperature range 300-10K up to 30 kOe magnetic field.

Fluoranthene-Based Molecules as Electron Transport and Blue Fluorescent Materials for Organic Light-Emitting Diodes

Herein we report the synthesis, characterization, and potential application of his (4- (7,9,10-triphenylfluoranthen-8-yl)pheny)sulfone (TPFDPSO2) and 2,8-bis (7,9,10-triphenylfluoranthen-8-yl) dibenzo b, d]-thiophene 5,5-dioxide (TPFDBTO2) as electron transport as well as light-emitting materials. These fluoranthene derivatives were synthesized by oxidation of their corresponding parent sulfide compounds, which were prepared via Diels-Alder reaction. These materials exhibit deep blue fluorescence emission in both solution and thin film, high photoluminescence quantum yield (PLQY), thermal and electrochemical stability over a wide potential range. Hole- and electron-only devices were fabricated to study the charge transport characteristics, and predominant electron transport property comparable with that of a well-known electron transport material, Alq(3), was observed. Furthermore, bilayer electroluminescent devices were fabricated utilizing these fluoranthene derivatives as electron transport as well as emitting layer, and device performance was compared with that of their parent sulfide molecules. The electroluminescence (EL) devices fabricated with these molecules displayed bright sky blue color emission and 5-fold improvement in external quantum efficiency (EQE) with respect to their parent compounds.

Zinc acetylacetonate hydrate adducted with nitrogen donor ligands: Synthesis, spectroscopic characterization, and thermal analysis

We report synthesis, spectroscopic characterization, and thermal analysis of zinc acetylacetonate complex adducted by nitrogen donor ligands, such as pyridine, bipyridine, and phenanthroline. The pyridine adducted complex crystallizes to monoclinic crystal structure, whereas other two adducted complexes have orthorhombic structure. Addition of nitrogen donor ligands enhances the thermal property of these complexes as that with parent metal-organic complex. Zinc acetylacetonate adducted with pyridine shows much higher volatility (106 degrees C), decomposition temperature (202 degrees C) as that with zinc acetylacetonate (136 degrees C, 220 degrees C), and other adducted complexes. All the adducted complexes are thermally stable, highly volatile and are considered to be suitable precursors for metal organic chemical vapor deposition. The formation of these complexes is confirmed by powder X-ray diffraction, Fourier transform infrared spectroscopy, mass spectroscopy, and elemental analysis. The complexes are widely used as starting precursor materials for the synthesis of ZnO nanostructures by microwave irradiation assisted coating process. (c) 2015 Elsevier B.V. All rights reserved.

Synthesis of Novel Benzofuran-Gathered C-2,4,6-substituted Pyrimidine Derivatives Conjugated by Sulfonyl Chlorides: Orally Bioavailable, Selective, Effective Antioxidants and Antimicrobials Drug Candidates

In the present study, we have made an effort to develop the novel synthetic antioxidants and antimicrobials with improved potency. The novel benzofuran-gathered C-2,4,6-substituted pyrimidine derivatives 5a, 5b, 5c, 5d, 5e, 5f, 6a, 6b, 6c, 6d, 6e, 6f, 7a, 7b, 7c, 7d, 7e, 7f, 8a, 8b, 8c, 8d, 8e, 8f, 9a, 9b, 9c, 9d, 9e, 9f were synthesized by simple and efficient four-step reaction pathway. Initially, o-alkyl derivative of salicylaldehyde readily furnish corresponding 2-acetyl benzofuran 2 in good yield, upon the treatment with potassium tertiary butoxide in the presence of molecular sieves. Further, Claisen-Schmidt condensation with aromatic aldehydes via treatment with thiourea followed by coupling reaction with different sulfonyl chlorides afforded target compounds. The structures of newly synthesized compounds were confirmed by IR, H-1 NMR, C-13 NMR, mass, and elemental analysis and further screened for their antioxidant and antimicrobial activities. The results showed that the synthesized compounds 8b, 8e, 9b, and 9e produced significant antioxidant activity with 50% inhibitory concentration higher than that of reference, whereas compounds 7d and 7c produced dominant antimicrobial activity at concentrations 1.0 and 0.5mg/mL compared with standard Gentamicin and Nystatin, respectively.

Ultra-small sulphur nanoparticles configured inside a flexible organic mixed conducting network as a cathode for lithium-sulphur batteries

The major challenges in Li-S batteries are the formation of soluble polysulphides during the reversible conversion of S-8 <-> Li2S, large changes in sulphur particle volume during lithiation and extremely poor charge transport in sulphur. We demonstrate here a novel and simple strategy to overcome these challenges towards practical realization of a stable high performance Li-S battery. For the first time, a strategy is developed which does away with the necessity of pre-fabricated high surface area hollow-structured adsorbates and also multiple nontrivial synthesis steps related to sulphur loading inside such adsorbates. A lithiated polyethylene glycol (PEG) based surfactant tethered on ultra-small sulphur nanoparticles and wrapped up with polyaniline (PAni) (abbreviated as S-MIEC) is demonstrated here as an exceptional cathode for Li-S batteries. The PEG and PAni network around the sulphur nanoparticles serves as an efficient flexible trap for sulphur and polysulphides and also provides distinct pathways for electrons (through PAni) and ions (through PEG) during battery operation. Contrary to the cathodes demonstrated based on various carbon-sulphur composites, the mixed conducting S-MIEC showed an extremely high loading of 75%. The S-MIEC exhibited a stable capacity of nearly 900 mA h g(-1) at the end of 100 cycles at a 1C current rate.

Catalytic Aldol-Cyclization Cascade of 3-Isothiocyanato Oxindoles with alpha-Ketophosphonates for the Enantioselective Synthesis of beta-Amino-alpha-hydroxyphosphonates

A cascade aldol cyclization reaction between 3-isothiocyanato oxindoles and alpha-ketophosphonates has been developed for the synthesis of beta-amino-alpha-hydroxyphosphonate derivatives. Catalyzed by a quinine-based tertiary amino-thiourea derivative, this reaction delivers 2-thioxooxazolidinyl phosphonates based on a spirooxindole scaffold bearing two contiguous quaternary stereogenic centers in high yields with excellent diastereo- (up to >20:1 dr) and enantioselectivities (up to >99:1 er).

Hydrogelation of bile acid-peptide conjugates and in situ synthesis of silver and gold nanoparticles in the hydrogel matrix

Fabricating supramolecular hydrogels with embedded metal nanostructures is important for the design of novel hybrid nanocomposite materials for diverse applications such as biosensing and chemosensing platforms, catalytic and antibacterial functional materials etc. Supramolecular self-assembly of bile acid-dipeptide conjugates has led to the formation of new supramolecular hydrogels. Gelation of these molecules depends strongly on the hydrophobic character of the bile acids. The possibility of in situ fabrication of Ag and Au NPs in these supramolecular hydrogels by incorporating Ag+ and Au3+ salts was investigated via photoreduction. Chemical reductions of Ag+ and Au3+ salts in the hydrogels were performed without adding any external stabilizing agents. In this report we have shown that the color, size and shape of silver nanoparticles formed by photoreduction depend on the amino acid residue of the side chain.

Single-step, size-controlled synthesis of colloidal silver nanoparticles stabilized by octadecylamine

A single step process for the synthesis of size-controlled silver nanoparticles has been developed using a bifunctional molecule, octadecylamine (ODA). Octadecylamine complexes to Ag+ ions electrostatically, reduce them, and subsequently stabilizes the nanoparticles thus formed. Hence, octadecylamine simultaneously functions as both a reducing and a stabilizing agent. The amine-capped nanoparticles can be obtained in the form of dry powder, which is readily redispersible in aqueous and organic solvents. The particle size, and the nucleation and growth kinetics of silver nanoparticles could be tuned by varying the molar ratio of ODA to AgNO3. The UV-vis spectra of nanoparticles prepared with different concentrations of ODA displayed the well-defined plasmon band with maximum absorption around 425 nm. The formation of silver metallic nanoparticles was confirmed by their XRD pattern. The binding of ODA molecule on the surface of silver has been studied by FT-IR and NMR spectroscopy. The formation of well-dispersed spherical Ag nanoparticles has been confirmed by TEM analysis. The particle size and distribution are found to be dependent on the molar concentration of the amine molecule. Open aperture z-scans have been performed to measure the nonlinearity of Ag nanoparticles. (C) 2015 Published by Elsevier B.V.

A new synthesis of Entacapone and report on related studies

A new synthesis of the catechol-O-methyltransferase (COMT) inhibitor, entacapone (E-isomer) has been achieved under mild conditions by amine-mediated demethylation of the precursor 2-Cyano-3-(3- hydroxy-4-methoxy-5-nitrophenyl) prop-2-eneamide, wherein the methoxyl group adjacent to a nitro group gets demethylated under nucleophilic attack. Similar demethylation was achieved on ethyl 2-cyano-3-(3, 4-dimethoxy-5-nitrophenyl) prop-2-enoate, 2-cyano-3-(3,4-dimethoxy-5-nitrophenyl)-N,N-diethylprop-2-enamide, ethyl 2-cyano-3-(3-hydroxy-4-methoxy-5-nitrophenyl) prop-2-enoate and ethyl 2-cyano-3-(4-methoxy-3-nitrophenyl) prop-2-enoate. The scope of demethylation has been studied. Analogues of ethyl 2-cyano-3-(3, 4-dimethoxy-5-nitrophenyl) prop-2-enoate wherein a methoxyl group is not adjacent to a NO (2) group are unaffected and phenolic derivatives yield the amine salts. Entacapone has been converted to salts with organic bases. The crystal structure of the isomer of entacapone (Z-isomer), a significant human metabolite of E-isomer has been established. NMR methods for deriving E and Z geometry and other similar molecules have been successfully established, mainly by studying the proton coupled C-13 spectra. Preliminary studies reveal in vitro activity for some compounds against tuberculosis (TB) and dengue.

Fluoranthene derivatives as blue fluorescent materials for non-doped organic light-emitting diodes

In this study, we report synthesis of symmetrically and non-symmetrically functionalized fluoranthene-based blue fluorescent molecular materials for non-doped electroluminescent devices. The solid state structure of these fluorophores has been established by single crystal X-ray diffraction analysis. Furthermore, a detailed experimental and theoretical study has been performed to understand the effect of substitution of symmetric and non-symmetric functional groups on optical, thermal and electrochemical properties of fluoranthene. These materials exhibit a deep blue emission and high PLQY in solution and solid state. The vacuum deposited, non-doped electroluminescent devices with the device structure ITO/NPD (15 nm)/CBP (15 nm)/EML (40 nm)/TPBI (30 nm)/LiF (1 nm)/Al were fabricated and characterized. A systematic shift in the peak position of EL emission was observed from sky blue to bluish-green with EL maxima from 477 nm to 490 nm due to different functional groups on the periphery of fluoranthene. In addition, a high luminance of >= 2000 cd m(-2) and encouraging external quantum efficiency (EQE) of 1.1-1.4% were achieved. A correlation of the molecular structure with device performance has been established.

Organic-inorganic hybrid PtCo nanoparticle with high electrocatalytic activity and durability for oxygen reduction

In Pt-transition metal (TM) alloy catalysts, the electron transfer from the TM to Pt is retarded owing to the inevitable oxidation of the TM surface by oxygen. In addition, acidic electrolytes such as those employed in fuel cells accelerate the dissolution of the surface TM oxide, which leads to catalyst degradation. Herein, we propose a novel synthesis strategy that selectively modifies the electronic structure of surface Co atoms with N-containing polymers, resulting in highly active and durable PtCo nanoparticle catalysts useful for the oxygen reduction reaction (ORR). The polymer, which is functionalized on carbon black, selectively interacts with the Co precursor, resulting in Co-N bond formation on the PtCo nanoparticle surface. Electron transfer from Co to Pt in the PtCo nanoparticles modified by the polymer is enhanced by the increase in the difference in electronegativity between Pt and Co compared with that in bare PtCo nanoparticles with the TM surface oxides. In addition, the dissolution of Co and Pt is prevented by the selective passivation of surface Co atoms and the decrease in the O-binding energy of surface Pt atoms. As a result, the catalytic activity and durability of PtCo nanoparticles for the ORR are significantly improved by the electronic ensemble effects. The proposed organic/inorganic hybrid concept will provide new insights into the tuning of nanomaterials consisting of heterogeneous metallic elements for various electrochemical and chemical applications.