P-type nitrogen-doped ZnO nanoparticles stable under ambient conditions

Zinc oxide is considered as a very promising material for optoelectronics. However, to date, the difficulty in producing stable p-type ZnO is a bottleneck, which hinders the advent of ZnO-based devices. In that context, nitrogen-doped zinc oxide receives much attention. However, numerous reviews report the controversial character of p-type conductivity in N-doped ZnO, and recent theoretical contributions explain that N-doping alone cannot lead to p-typeness in Zn-rich ZnO. We report here that the ammonolysis at low temperature of ZnO(2) yields pure wurtzite-type N-doped ZnO nanoparticles with an extraordinarily large amount of Zn vacancies (up to 20%). Electrochemical and transient spectroscopy studies demonstrate that these Zn-poor nanoparticles exhibit a p-type conductivity that is stable over more than 2 years under ambient conditions.     

Development and validation of HPLC method for simultaneous estimation of piperine and guggulsterones in compound Unani formulation (tablets) and a nanoreservoir system

An attempt has been made to develop and validate a simultaneous HPLC method for novel approach of drug release via oil‐in‐water (o/w) nanoemulsion formulation and Habb‐e‐Khardal Unani tablet containing piperine and guggul sterones E and Z as main ingredients. Nanoemulsion was prepared by titration method using sefsol‐218 as an oily phase, cremophor‐EL as a surfactant, transcutol as a co‐surfactant and distilled water as an aqueous phase. The formulation was optimized on the basis of thermodynamic stability and dispersibilty test. The nanoformulation was evaluated for particle size, surface morphology, electrical conductivity and viscosity determination. The in vitro dissolution was carried out by dialysis bag method. Drugs were quantified using an HPLC method developed in‐house with a C₁₈ column as stationary phase and acetonitrile and water as mobile phase at λ_max of 240 nm. The optimized formulation showed higher drug release, lower droplet size and less viscosity as compared with the conventional Habb‐e‐Khardal Unani tablet. The present study illustrated the potential of nanoemulsion dosage form in improving biopharmaceutic performance of piperine and guggul sterone. The HPLC method was also found to be quite sufficient for the routine quality control of formulations containing piperine and guggul sterone E and Z as ingredients and also for in vitro drug release studies. Copyright © 2011 John Wiley & Sons, Ltd.     

A Structural Study of Epoxidized Natural Rubber (ENR-50) and Its Cyclic Dithiocarbonate Derivative Using NMR Spectroscopy Techniques

A structural study of epoxidized natural rubber (ENR-50) and its cyclic dithiocarbonate derivative was carried out using NMR spectroscopy techniques. The overlapping ¹H-NMR signals of ENR-50 at δ 1.56, 1.68-1.70, 2.06, 2.15-2.17 ppm were successfully assigned. In this work, the ¹³C-NMR chemical shift assignments of ENR-50 were consistent to the previously reported work. A cyclic dithiocarbonate derivative of ENR-50 was synthesized from the reaction of purified ENR-50 with carbon disulfide (CS₂), in the presence of 4-dimethylaminopyridine (DMAP) as catalyst at reflux temperature. The cyclic dithiocarbonate formation involved the epoxide ring opening of the ENR-50. This was followed by insertion of the C-S moiety of CS₂ at the oxygen attached to the quaternary carbon and methine carbon of epoxidized isoprene unit, respectively. The bands due to the C=S and C-O were clearly observed in the FTIR spectrum while the ¹H-NMR spectrum of the derivative revealed the peak attributed to the methylene protons had split. The ¹³C-NMR spectrum of the derivative further indicates two new carbon peaks arising from the >C=S and quaternary carbon of cyclic dithiocarbonate. All other ¹H- and ¹³C-NMR chemical shifts of the derivative remain unchanged with respect to the ENR-50.     

Anti-HIV-1 and cytotoxicity of the alkaloids of Erythrina abyssinica Lam. growing in Sudan

Erythrina abyssinica Lam. is an important medicinal plant growing in Sudan; its seeds were investigated for the first time for their alkaloidal constituents and biological activity. The in vitro cytotoxicity of the crude alkaloidal fraction (CAF) against the cell lines HeLa, Hep-G2, HEP-2, HCT116, MCF-7 and HFB4 showed promising activity, with IC?? values of 13.8, 10.1, 8.16, 13.9, 11.4 and 12.2?μg?mL?1, respectively. Doxorubicin (positive control) showed in vitro cytotoxic activity with IC?? values 3.64, 4.57, 4.89, 3.74, 2.97 and 3.96?μg?mL?1, respectively. Bioassay-guided fractionation and isolation of the CAF led to the isolation of five Erythrina alkaloids, identified as erythraline, erysodine, erysotrine, 8-oxoerythraline and 11-methoxyerysodine. These were evaluated for their in vitro cytotoxic activity against Hep-G2 which resulted in IC?? values 17.60, 11.80, 15.80, 3.89 and 11.40?μg?mL?1, respectively. Furthermore, in vitro cytotoxic activity against HEP-2 was evaluated, which resulted in IC?? values 15.90, 19.90, 21.60, 18.50 and 11.50?μg?mL?1, respectively. The CAF caused a reduction in the viability of mock-infected MT-4 cells with a CC?? of 53?μM and a 50% protection of MT-4 cells against HIV-1 induced cytopathogeneticy with a EC?? of >53?μM, compared with EFV as a positive control, which had a CC?? of 45?μM and an EC?? of 0.003?μM. We concluded that the isolated alkaloids were responsible for the carcinogenic actions of the plant extract previously reported in the literature.     

Flexible microfluidic cloth-based analytical devices using a low-cost wax patterning technique

This paper describes the fabrication of microfluidic cloth-based analytical devices (μCADs) using a simple wax patterning method on cotton cloth for performing colorimetric bioassays. Commercial cotton cloth fabric is proposed as a new inexpensive, lightweight, and flexible platform for fabricating two- (2D) and three-dimensional (3D) microfluidic systems. We demonstrated that the wicking property of the cotton microfluidic channel can be improved by scouring in soda ash (Na(2)CO(3)) solution which will remove the natural surface wax and expose the underlying texture of the cellulose fiber. After this treatment, we fabricated narrow hydrophilic channels with hydrophobic barriers made from patterned wax to define the 2D microfluidic devices. The designed pattern is carved on wax-impregnated paper, and subsequently transferred to attached cotton cloth by heat treatment. To further obtain 3D microfluidic devices having multiple layers of pattern, a single layer of wax patterned cloth can be folded along a predefined folding line and subsequently pressed using mechanical force. All the fabrication steps are simple and low cost since no special equipment is required. Diagnostic application of cloth-based devices is shown by the development of simple devices that wick and distribute microvolumes of simulated body fluids along the hydrophilic channels into reaction zones to react with analytical reagents. Colorimetric detection of bovine serum albumin (BSA) in artificial urine is carried out by direct visual observation of bromophenol blue (BPB) colour change in the reaction zones. Finally, we show the flexibility of the novel microfluidic platform by conducting a similar reaction in a bent pinned μCAD.     

Water-wire catalysis in photoinduced acid-base reactions

The pronounced ability of water to form a hyperdense hydrogen (H)-bond network among itself is at the heart of its exceptional properties. Due to the unique H-bonding capability and amphoteric nature, water is not only a passive medium, but also behaves as an active participant in many chemical and biological reactions. Here, we reveal the catalytic role of a short water wire, composed of two (or three) water molecules, in model aqueous acid-base reactions synthesizing 7-hydroxyquinoline derivatives. Utilizing femtosecond-resolved fluorescence spectroscopy, we tracked the trajectories of excited-state proton transfer and discovered that proton hopping along the water wire accomplishes the reaction more efficiently compared to the transfer occurring with bulk water clusters. Our finding suggests that the directionality of the proton movements along the charge-gradient H-bond network may be a key element for long-distance proton translocation in biological systems, as the H-bond networks wiring acidic and basic sites distal to each other can provide a shortcut for a proton in searching a global minimum on a complex energy landscape to its destination.     

Polymer/boron nitride nanocomposite materials for superior thermal transport performance

Boron nitride nanosheets were dispersed in polymers to give composite films with excellent thermal transport performances approaching the record values found in polymer/graphene nanocomposites. Similarly high performance at lower BN loadings was achieved by aligning the nanosheets in poly(vinyl alcohol) matrix by simple mechanical stretching (see picture).     

New Metal Oxamates as Precursors of Low-Dimensional Heterobimetallics

The goal of this work was to synthesize new molecular bricks which could be used as precursors of heterobimetallic low-dimensional compounds. Along this line, four compounds have been synthesized and structurally characterized, namely (NBu(4))(2)[Ni(Cl(2)opba)] (1), (NBu(4))(2)[Cu(Cl(2)opba)] (2), (NBu(4))(5)[Mn(Cl(2)opba)(DMSO)(2)](4) (3), and Cu(en)(2)[Mn(Cl(2)opba)(H(2)O)(2)](2).2DMSO (4), with Cl(2)opba = (4,5-dichloro-o-phenylene)bis(oxamato), NBu(4) = tetra-n-butylammonium, en = ethylenediamine, and DMSO = dimethyl sulfoxide. Compounds 1 and 2 are isostructural; they crystallize in the monoclinic system, space group C2/c, Z = 4, with a = 18.708(2) ?, b = 17.525(2) ?, c = 14.763(9) ?, and beta = 92.03(4) degrees for 1 and a = 18.928(2) ?, b = 17.634(2) ?, c = 14.704(9) ?, and beta = 92.38(3) degrees for 2. 3 crystallizes in the tetragonal system, space group P&fourmacr;2(1)c, Z = 2, with a = 26.295(10) ? and c = 12.342(7) ?. The structure shows a random occupation of the metal site by Mn(III) and Mn(II) ions in 3/4 and 1/4 ratios, respectively. 4 crystallizes in the triclinic system, space group P&onemacr;, Z = 1, with a = 7.066(7) ?, b = 11.844(1) ?, c = 14.292(5) ?, alpha = 105.64(2) degrees, beta = 97.67(5) degrees, and gamma = 102.13(3) degrees. The structure consists of Mn(III)Cu(II)Mn(III) trinuclear species, with Cu-O-Mn bridges involving oxygen atoms of the oxamato groups already linked to the metal atom. The magnetic properties of compounds 1-4 have been investigated and quantitatively interpreted. For 3, this magnetic investigation has been performed on a single crystal, which allows us to determine unambiguously the sign of the axial zero-field splitting parameter for the Mn(III) ion. The potentialities of these new molecular bricks have been discussed.     

Coumarin-based D–π–A dyes for efficient DSSCs: DFT and TD-DFT study of the π-spacers influence on photovoltaic properties

Research on Chemical Intermediates - A series of D–π–A architectures dyes with Coumarin-based derivatives as difluorenylaminocoumarin (DF) and diphenylaminocoumarin (DP) have been...     

Stability, rheological, magnetorheological and volumetric characterizations of polymer based magnetic nanofluids

The Fe₃O₄ nanoparticles and Fe₃O₄ nanoparticles coated with oleic acid have been dispersed in base fluid of poly(ethylene glycol) (PEG). Stability and particle size distribution of these nanofluids have been studied by result analysis of UV–Vis spectroscopy, zeta potential and dynamic light scattering. Blue shift of UV–Vis spectra has been related to quantum effects such as band gap enlargement with particle size decreasing and also to effect of oleic acid on the ultraviolet wavelength. Flow behavior and suspension structure of Fe₃O₄ nanoparticles dispersed in PEG have been determined by rheological properties. Viscosity values of Fe₃O₄-PEG nanofluid as a function of temperature have also been investigated. The chain-like structure of Fe₃O₄ nanoparticles coated with oleic acid in base fluid of PEG has been verified by measuring the magnetorheological properties. The effect of temperature on magnetorheological properties of Fe₃O₄ nanoparticles coated with oleic acid has also been investigated in base fluid of PEG. The volumetric properties of Fe₃O₄-PEG and Fe₃O₄ coated with oleic acid–PEG nanofluids and PEG–oleic acid solution have also been measured at different temperatures to specify the suspension structure and also interactions of Fe₃O₄, PEG and oleic acid molecules.