Axial and equatorial ligand effects on biomimetic cysteine dioxygenase model complexes

Density functional theory (DFT) calculations are presented on biomimetic model complexes of cysteine dioxygenase and focus on the effect of axial and equatorial ligand placement. Recent studies by one of us [Y. M. Badiei, M. A. Siegler and D. P. Goldberg, J. Am. Chem. Soc. 2011, 133, 1274] gave evidence of a nonheme iron biomimetic model of cysteine dioxygenase using an i-propyl-bis(imino)pyridine, equatorial tridentate ligand. Addition of thiophenol, an anion - either chloride or triflate - and molecular oxygen, led to several possible stereoisomers of this cysteine dioxygenase biomimetic complex. Moreover, large differences in reactivity using chloride as compared to triflate as the binding anion were observed. Here we present a series of DFT calculations on the origin of these reactivity differences and show that it is caused by the preference of coordination site of anion versus thiophenol binding to the chemical system. Thus, stereochemical interactions of triflate and the bulky iso-propyl substituents of the ligand prevent binding of thiophenol in the trans position using triflate. By contrast, smaller anions, such as chloride, can bind in either cis or trans ligand positions and give isomers with similar stability. Our calculations help to explain the observance of thiophenol dioxygenation by this biomimetic system and gives details of the reactivity differences of ligated chloride versus triflate.     

Assembly of one dimensional inorganic nanostructures into functional 2D and 3D architectures. Synthesis, arrangement and functionality

This review will focus on the synthesis, arrangement, structural assembly, for current and future applications, of 1D nanomaterials (tubes, wires, rods) in 2D and 3D ordered arrangements. The ability to synthesize and arrange one dimensional nanomaterials into ordered 2D or 3D micro or macro sized structures is of utmost importance in developing new devices and applications of these materials. Micro and macro sized architectures based on such 1D nanomaterials (e.g. tubes, wires, rods) provide a platform to integrate nanostructures at a larger and thus manageable scale into high performance electronic devices like field effect transistors, as chemo- and biosensors, catalysts, or in energy material applications. Carbon based, metal oxide and metal based 1D arranged materials as well as hybrid or composite 1D materials of the latter provide a broad materials platform, offering a perspective for new entries into fascinating structures and future applications of such assembled architectures. These architectures allow bridging the gap between 1D nanostructures and the micro and macro world and are the basis for an assembly of 1D materials into higher hierarchy domains. This critical review is intended to provide an interesting starting point to view the current state of the art and show perspectives for future developments in this field. The emphasis is on selected nanomaterials and the possibilities for building three dimensional arrays starting from one dimensional building blocks. Carbon nanotubes, metal oxide nanotubes and nanowires (e.g. ZnO, TiO(2), V(2)O(5), Cu(2)O, NiO, Fe(2)O(3)), silicon and germanium nanowires, and group III-V or II-VI based 1D semiconductor nanostructures like GaS and GaN, pure metals as well as 1D hybrid materials and their higher organized architectures (foremost in 3D) will be focussed. These materials have been the most intensively studied within the last 5-10 years with respect to nano-micro integration aspects and their functional and application oriented properties. The critical review should be interesting for a broader scientific community (chemists, physicists, material scientists) interested in synthetic and functional material aspects of 1D materials as well as their integration into next higher organized architectures.     

Synergic effect of multi-walled carbon nanotubes and gold nanoparticles towards immunosensing of ricin with carbon nanotube-gold nanoparticles-chitosan modified screen printed electrode

An amperometric immunosensor for the specific detection of Ricinus communis is reported. Screen printed electrodes (SPEs) were modified with gold nanoparticles (GNPs) loaded multiwalled carbon nanotubes (MWCNTs)-chitosan (Ch) film. The ratio of MWCNT and GNP was optimised to get best electrochemically active electrode. Sandwich immunoassay format was used for the immunosensing of ricin. The revealing antibodies tagged with the enzyme alkaline phosphatase (ALP) converts the substrate 1-naphthyl phosphate into 1-naphthol that was determined with the amperometric technique. The amperometric current obtained was correlated with the concentration of ricin. The prepared GNP-MWCNT-Ch-SPE showed high stability due to the Ch film, short response time with good reproducibility and increased shelf life of the electrodes immobilised with antibodies. The electrochemical activity of the electrode improved because of optimization of composition of CNTs and gold nanoparticles. Under the optimal conditions, the modified electrode showed a wide linear response to the concentration of ricin in the range of 2.5-25 ng mL(-1) with a limit of detection of 2.1 ng mL(-1) and with a relative standard deviation of 5.1% and storage life of 32 days.     

Cerium oxide nanoparticles scavenge nitric oxide radical (˙NO)

In this study we have obtained evidence that cerium oxide nanoparticles (CeO(2) NPs) are able to scavenge nitric oxide radical. Surprisingly, this activity is present in CeO(2) NPs with a lower level of cerium in the 3+ state (CeO(2) NPs with low 3+/4+ ratio and therefore a reduced number of oxygen vacancies), in contrast to the superoxide scavenging properties which are correlated with an increased level of cerium in the 3+ state (CeO(2) NPs with high 3+/4+ ratio and therefore an increased number of oxygen vacancies).     

Fluoranthene based fluorescent chemosensors for detection of explosive nitroaromatics

A novel fluoranthene based fluorescent chemosensor for the detection of picric acid (PA) at the parts per billion (ppb) level was evaluated. Static fluorescence quenching was the dominant process by intercalative π-π interaction between fluoranthene (S(1)) and nitroaromatics.     

Imino-phenolic-pyridyl conjugates of calix[4]arene (L1 and L2) as primary fluorescence switch-on sensors for Zn2+ in solution and in HeLa cells and the recognition of pyrophosphate and ATP by [ZnL2

Pyridyl-based triazole-linked calix[4]arene conjugates, viz. L(1) and L(2), were synthesized and characterized. These two conjugates were shown to be selective and sensitive for Zn(2+) among the 12 metal ions studied in HEPES buffer medium by fluorescence, absorption, and visual color change with the detection limit of ~31 and ~112 ppb, respectively, by L(1) and L(2). Moreover, the utility of the conjugates L(1) and L(2) in showing the zinc recognition in live cells has also been demonstrated using HeLa cells as monitored by fluorescence imaging. The zinc complexes of L(1) and L(2) were isolated, and the structure of [ZnL(1)] has been established by single-crystal XRD and that of [ZnL(2)] by DFT calculations. TDDFT calculations were performed in order to demonstrate the electronic properties of receptors and their zinc complexes. The isolated zinc complexes, viz. [ZnL(1)] and [ZnL(2)], have been used as molecular tools for the recognition of anions on the basis of their binding affinities toward Zn(2+). [ZnL(2)] was found to be sensitive and selective toward phosphate-bearing ions and molecules and in particular to pyrophosphate (PPi) and ATP among the other 18 anions studied; however, [ZnL(1)] was not sensitive toward any of the anions studied. The selectivity has been shown on the basis of the changes observed in the emission and absorption spectral studies through the removal of Zn(2+) from [ZnL(2)] by PPi. Thus, [ZnL(2)] has been shown to detect PPi up to 278 ± 10 ppb at pH 7.4 in aqueous methanolic (1/2 v/v) HEPES buffer.     

Development and Validation of a Liquid Chromatographic Method for Determination of Efavirenz in Human Plasma

A simple, rapid, and sensitive high-performance liquid chromatographic method for estimation of efavirenz in human plasma has been developed and validated. Chromatography was performed with C₁₈ analytical column and 50:50 acetonitrile–phosphate buffer (pH 3.5) as mobile phase. Compounds were monitored by UV detection at 247 nm. The retention time for efavirenz was 6.45 min and that for the internal standard, nelfinavir, was 2.042 min. Response was a linear over the concentration range of 0.1 μg–10 μg mL⁻¹ in human plasma. The method was simple, specific, precise and accurate and was useful for bioequivalence and pharmacokinetic studies of efavirenz.     

Synthesis of flower-like gold nanoparticles and their electrocatalytic activity towards the oxidation of methanol and the reduction of oxygen

This article describes the synthesis of branched flower-like gold (Au) nanocrystals and their electrocatalytic activity toward the oxidation of methanol and the reduction of oxygen. Gold nanoflowers (GNFs) were obtained by a one-pot synthesis using N-2-hydroxyethylpiperazine-N-2-ethanesulphonic acid (HEPES) as a reducing/stabilizing agent. The GNFs have been characterized by UV-visible spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), and electrochemical measurements. The UV-visible spectra show two bands corresponding to the transverse and longitudinal surface plasmon (SP) absorption at 532 and 720 nm, respectively, for the colloidal GNFs. The GNFs were self-assembled on a sol-gel-derived silicate network, which was preassembled on a polycrystalline Au electrode and used for electrocatalytic applications. The GNFs retain their morphology on the silicate network; the UV-visible diffuse reflectance spectra (DRS) of GNFs on the silicate network show longitudinal and transverse bands as in the case of colloidal GNFs. The GNFs show excellent electrocatalytic activity toward the oxidation of methanol and the reduction of oxygen. Oxidation of methanol in alkaline solution was observed at approximately 0.245 V, which is much less positive than that on an unmodified polycrystalline gold electrode. Reduction of oxygen to H2O2 and the further reduction of H2O2 to water in neutral pH were observed at less negative potentials on the GNFs electrode. The electrocatalytic activity of GNFs is significantly higher than that of the spherically shaped citrate-stabilized Au nanoparticles (SGNs).     

Electronic, epr and magnetic studies of Co(II), Ni(II) and Cu(II) complexes with thiosemicarbazone (L1) and semicarbazone (L2) derived from pyrole-2-carboxyaldehyde

Co(II), Ni(II) and Cu(II) complexes are synthesized with thiosemicarbazone (L(1)) and semicarbazone (L(2)) derived from pyrole-2-carboxyaldehyde. These complexes are characterized by elemental analysis, molar conductance, magnetic susceptibility measurements, mass, IR, electronic and EPR spectral studies .The molar conductance measurements of the complexes in DMSO correspond to non-electrolytic nature except Co(L1)2(NO3)2 and Ni(L1)2(NO3)2 complexes which are 1:2 electrolytes. All the complexes are of high-spin type. On the basis of spectral studies an octahedral geometry may be assigned for Co(II) and Ni(II) complexes except Co(L1)2(NO3)2 and Ni(L1)2(NO3)2 which are of tetrahedral geometry. A tetragonal geometry may be suggested for Cu(II) complexes.