UV-vis-NIR and EPR characterisation of the redox series [MQ(3)](2+,+,0,-,2-), M = Ru or Os, and Q = o-quinone derivative

The neutral title compounds with Q = 3,5-di-tert-butyl-o-quinone or 4,6-di-tert-butyl-N-phenyl-o-iminobenzoquinone (Q(x)) were studied by UV-vis-NIR spectroelectrochemistry and by EPR spectroscopy in the case of the odd-electron monocation and monoanion intermediates. Supported by DFT and TD-DFT calculations, the results indicate stepwise electron removal from predominantly ligand-based delocalised MOs on oxidation whereas the stepwise electron uptake on reduction involves unoccupied MOs with considerably metal-ligand mixed character. In both cases, the strong near-infrared absorption of the neutral precursors diminishes. In comparison to the ruthenium series, the osmium analogues exhibit larger transition energies from enhanced MO splitting and a different EPR response due to the higher spin-orbit coupling. The main difference between the quinone (1(n), 2(n)) and corresponding monoiminoquinone systems (3(n), 4(n)) is the shift of about 0.6 V to lower potentials for the monoimino analogues. While the absorption features do not differ markedly, the EPR data reflect a higher degree of covalent bonding for the complexes with monoimino ligands.     

Selective recognition of fluoride and acetate by a newly designed ruthenium framework: experimental and theoretical investigations

An effective anion sensor, [Ru(II)(bpy)(2)(H(2)L(-))](+) (1(+)), based on a redox and photoactive {Ru(II)(bpy)(2)} moiety and a new ligand (H(3)L = 5-(1H-benzo[d]imidazol-2-yl)-1H-imidazole-4-carboxylic acid), has been developed for selective recognition of fluoride (F(-)) and acetate (OAc(-)) ions. Crystal structures of the free ligand, H(3)L and [1](ClO(4)) reveal the existence of strong intramolecular and intermolecular hydrogen bonding interactions. The structure of [1](ClO(4)) shows that the benzimidazole N-H of H(2)L(-) is hydrogen bonded with the pendant carboxylate oxygen while the imidazole N-H remains free for possible hydrogen bonding interaction with the anions. The potential anion sensing features of 1(+) have been studied by different experimental and theoretical (DFT) investigations using a wide variety of anions, such as F(-), Cl(-), Br(-), I(-), HSO(4)(-), H(2)PO(4)(-), OAc(-) and SCN(-). Cyclic voltammetry and differential pulse voltammetry established that 1(+) is an excellent electrochemical sensor for the selective recognition of F(-) and OAc(-) anions. 1(+) is also found to be a selective colorimetric sensor for F(-) or OAc(-) anions where the MLCT band of the receptor at 498 nm is red shifted to 538 nm in the presence of one equivalent of F(-) or OAc(-) with a distinct change in colour from reddish-orange to pink. The binding constant between 1(+) and F(-) or OAc(-) has been determined to be logK = 7.61 or 7.88, respectively, based on spectrophotometric titration in CH(3)CN. The quenching of the emission band of 1(+) at 716 nm (λ(ex) = 440 nm, Φ = 0.01 at 298 K in CH(3)CN) in the presence of one equivalent of F(-) or OAc(-), as well as two distinct lifetimes of the quenched and unquenched forms of the receptor 1(+), makes it also a suitable fluorescence-based sensor. All the above experiments, in combination with (1)H NMR, suggest the formation of a 1:1 adduct between the receptor (1(+)) and the anion (F(-) or OAc(-)). The formation of 1:1 adduct {[1(+)·F(-)] or [1(+)·OAc(-)]} has been further evidenced by in situ ESI-MS(+) in CH(3)CN. Though the receptor, 1(+), is comprised of two N-H protons associated with the coordinated H(2)L(-) ligand, only the free imidazole N-H proton participates in the hydrogen bonding interactions with the incoming anions, while the intramolecularly hydrogen bonded benzimidazole N-H proton remains intact as evidenced by the crystal structure of the final product (1). The hydrogen bond mediated anion sensing mechanism, over the direct deprotonation pathway, in 1(+) has been further justified by a DFT study and subsequent NBO analysis.     

Anticancer β-hairpin peptides: membrane-induced folding triggers activity

Several cationic antimicrobial peptides (AMPs) have recently been shown to display anticancer activity via a mechanism that usually entails the disruption of cancer cell membranes. In this work, we designed an 18-residue anticancer peptide, SVS-1, whose mechanism of action is designed to take advantage of the aberrant lipid composition presented on the outer leaflet of cancer cell membranes, which makes the surface of these cells electronegative relative to the surface of noncancerous cells. SVS-1 is designed to remain unfolded and inactive in aqueous solution but to preferentially fold at the surface of cancer cells, adopting an amphiphilic β-hairpin structure capable of membrane disruption. Membrane-induced folding is driven by electrostatic interaction between the peptide and the negatively charged membrane surface of cancer cells. SVS-1 is active against a variety of cancer cell lines such as A549 (lung carcinoma), KB (epidermal carcinoma), MCF-7 (breast carcinoma), and MDA-MB-436 (breast carcinoma). However, the cytotoxicity toward noncancerous cells having typical membrane compositions, such as HUVEC and erythrocytes, is low. CD spectroscopy, appropriately designed peptide controls, cell-based studies, liposome leakage assays, and electron microscopy support the intended mechanism of action, which leads to preferential killing of cancerous cells.     

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.     

"Turn on" electron-transfer-based selective detection of ascorbic acid via copper complexes immobilized on glass

"Turn-on" optical detection of parts-per-million (ppm) levels of ascorbic acid (AA) in water has been determined using a redox-active monolayer on glass.     

Magnetoresistance studies of MeV ranged H and C ion irradiated HOPG flakes

2 MeV protons and 1 MeV carbon ions are bombarded on highly oriented pyrolytic graphite (HOPG) samples and their electronic transport measurements are carried out in the presence of magnetic field. The Magneto-Resistance (MR) measurements show measurable hysteresis in the resistance value after ion beam irradiation for the in-plane magnetic field direction as well as for the out-of-plane field direction. The MR depends on the thickness of the flake and the method of its separation from the bulk HOPG. The results substantiate that the ferromagnetic coupling between the magnetic moments at the vacancy defect sites in HOPG sensitively depends on the average defect separation. The average defect separation range of 1.7–0.5 nm allows only a part of the 40 μm thick proton beam irradiated sample to go for ferromagnetic ordering. Similar conclusions are drawn from carbon ion irradiated HOPG flake. The irradiation increases the resistance of the flake as well.     

Range‐independent background subtraction algorithm for recovery of Raman spectra of biological tissue

An important requirement for the use of Raman spectroscopy for tissue diagnostic applications is an appropriate algorithm that can faithfully retrieve weak tissue Raman signals from the measured raw Raman spectra. Although iterative modified polynomial‐fitting‐based automated algorithms are widely used, these are sensitive to the choice of the fitting range, thereby leading to significantly different Raman spectra for different start and stop wavenumber selection. We report here an algorithm for automated recovery of the weak Raman signal, which is range independent. Given a raw Raman spectrum and the choice of the start and the stop wavenumbers, the algorithm first truncates the spectrum to include the raw data within this wavenumber range, linearly extrapolates the truncated raw spectrum beyond the points of truncation on the two sides by using coefficients of linear least‐square fit, adds two Gaussian peaks of appropriate height and width on the extrapolated linear wings on either side and then iteratively smoothens the data with all these add‐ons such that the smaller of the ordinate values of the smoothed and the starting raw data serve as the input to each successive round of iterative smoothing until the added Gaussian peaks are fully recovered. The algorithm was compared with the modified polynomial‐based algorithms using mathematically simulated Raman spectrum as well as experimentally measured Raman spectra from various biological samples and was found to yield consistently range‐independent and artifact‐free Raman signal with zero baseline. Copyright © 2012 John Wiley & Sons, Ltd.     

A lattice dynamical investigation for the Raman and the infrared frequencies of Bi2W2O9

Studies on infrared and Raman-active phonons in the Aurivillius ferroelectric Bi₂W₂O₉ were performed theoretically. The Raman and infrared phonons were calculated by applying a short-range force constant model using normal coordinates having space group Pna2₁. Sixteen stretching, two repulsive and seventeen bending force constants were used for the calculations of the zone center phonons. The calculated Raman and infrared wavenumbers are in very good agreement with the experimental ones in the literature. Potential energy distribution for this compound has also been investigated for the contribution of each force constant towards the Raman and the infrared wavenumbers.     

Carrier dynamics in type-II GaAsSb/GaAs quantum wells

Time-resolved photoluminescence (PL) characteristics of type-II GaAsSb/GaAs quantum wells are presented. The PL kinetics are determined by the dynamic band bending effect and the distribution of localized centers below the quantum well band gap. The dynamic band bending results from the spatially separated electron and hole distribution functions evolving in time. It strongly depends on the optical pump power density and causes temporal renormalization of the quantum well ground-state energy occurring a few nanoseconds after the optical pulse excitation. Moreover, it alters the optical transition oscillator strength. The measured PL lifetime is 4.5 ns. We point out the critical role of the charge transfer processes between the quantum well and localized centers, which accelerate the quantum well photoluminescence decay at low temperature. However, at elevated temperatures the thermally activated back transfer process slows down the quantum well photoluminescence kinetics. A three-level rate equation model is proposed to explain these observations.     

Anomalous variation of the Lamb-M?ssbauer factor at the magnetic transition temperature in magnetoelectric?GaFeO(3)

Temperature-dependent (57)Fe M?ssbauer spectroscopy (5-723?K) and neutron diffraction (2-290?K) measurements are carried out on polycrystalline magnetoelectric GaFeO(3). From the neutron diffraction data, evidence for the magnetostriction and increased disorder at Fe sites close to the ferrimagnetic Curie transition temperature (T(C)) is observed. From the M?ssbauer data, it is observed that the Lamb-M?ssbauer factor as a function of temperature f(T), which is related to the integral over the first Brillouin zone of the phonon spectrum, shows a unequivocal variation at the T(C). The observations are discussed in terms of spin-phonon coupling. The observed average hyperfine fields from (57)Fe M?ssbauer spectra match with the bulk magnetization data. A critical exponent (β) of 0.38?±?0.02 and a Debye temperature (θ(D)) of ～350?K is estimated from the (57)Fe M?ssbauer data.