The gas-phase on-line production of vanadium oxytrihalides, VOX3 and their identification by infrared spectroscopy

A new route has been devised, leading to the production of VOX₃ molecules where X=F, Br and I by an on-line process using vanadium oxytrichloride, VOCl₃ as a starting compound passed over the following heated salts NaF, KBr and KI at 375, 700 and 550°C, respectively. The products have been characterized by the IR spectra of their vapors. The low resolution gas phase on-line Fourier transform infrared spectra reported for the first time show strong bands with PQR type structure, centered at 1058, 1035, 1030 and 1025 cm⁻¹ assigned to the ν₁(a₁), the O=V stretching fundamental mode of VOF₃, VOCl₃, VOBr₃ and VOI₃, respectively.     

Mass spectrometric study of the dissociation of Group XI metal complexes with fatty acids and glycerolipids: Ag2H+ and Cu2H+ ion formation in the presence of a double bond

Results of mass spectrometric studies are reported for the collisional dissociation of Group XI (Cu, Ag, Au) metal ion complexes with fatty acids (palmitic, oleic, linoleic and α-linolenic) and glycerolipids. Remarkably, the formation of M₂H⁺ ions (M = Cu, Ag) is observed as a dissociation product of the ion complexes containing more than one metal cation and only if the lipid in the complex contains a double bond. Ag₂H⁺ is formed as the main dissociation channel for all three of the fatty acids containing double bonds that were investigated while Cu₂H⁺ is formed with one of the fatty acids and, although abundant, is not the dominant dissociation channel. Also, Cu(I) and Ag(I) ion complexes were observed with glycerolipids (including triacylglycerols and glycerophospholipids) containing either saturated or unsaturated fatty acid substituents. Interestingly, Ag₂H⁺ ion is formed in a major fragmentation channel with the lipids that are able to form the complex with two metal cations (triacylglycerols and glycerophosphoglycerols), while lipids containing a fixed positive charge (glycerophospocholines) complex only with a single metal cation. The formation of Ag₂H⁺ ion is a significant dissociation channel from the complex ion [Ag₂(L–H)]⁺ where L = Glycerophospholipid (GP) (18:1/18:1). Cu(I) also forms complexes of two metal cations with glycerophospholipids but these do not produce Cu₂H⁺ upon dissociation. Rather organic fragments, not containing Cu(I), are formed, perhaps due to different interactions of these metal cations with lipids resulting from the much smaller ionic radius of Cu(I) compared to Ag(I).     

Solvation Phenomena of Potassium Thiocyanate in Methanol–Water Mixtures

This paper reports the results of a variety of experiments carried out for understanding the solvation behavior of potassium thiocyanate in methanol–water mixtures. Electrical conductivity, speed of sound, viscosity, and FT-Raman spectra of potassium thiocyanate solutions in 5 and 10% methanol–water (w/w) mixtures were measured as functions of concentration and temperature. The conductivity and structural relaxation time suggest the ion–solvent and solvent-separated ion–ion associations increase as the salt concentration increases in the mixtures. The Raman band shifts due to the C–O stretching mode of methanol for the solvent mixtures reveal the formation of methanol–water complexes. The significant changes in the Raman bands for the C–N, C–S and O–H stretching modes indicate the presence of SCN⁻−solvent interactions through the N-end, “free” SCN⁻ and the solvent-shared ion pairs as potassium thiocyanate is added to the methanol–water mixtures. The relative changes corresponding to H–O–H bending and C–O stretching frequencies indicate that K⁺ is preferentially solvated by water in these solvent mixtures. The appearance and increase of the intensity of a broad band at ≈940 cm⁻¹ upon salt addition was attributed to the SCN⁻–H₂O–K⁺ solvent-shared ion pairs. No Raman spectral evidence for K⁺(H₂O)_n species was observed. The preferential solvation of K⁺ and SCN⁻ in the methanol−water mixtures was verified by the application of the Kirkwood−Buff theory of solutions. This theory confirms that K⁺ is strongly preferentially solvated by water, whereas SCN⁻ is preferentially solvated by the methanol component.     

Incorporation of ferrocene into polypyrrole films via an ionic adduct with boron trifluoride

1-(Ferrocenyl)ethanol has been immobilized within polypyrrole films during their electrochemical deposition, or following their deposition, via its adduct with boron trifluoride. Dissociation of H⁺ from this adduct, formed in a solution of boron trifluoride diethyl ether (BFEE) in acetonitrile, produces an anion that can act as a counterion for oxidized polypyrrole. Its subsequent hydrolysis produces a polypyrrole film containing neutral 1-(ferrocenyl)ethanol which was found to be strongly retained. In addition to producing a novel type of polypyrrole–ferrocene composite, this work provides clear evidence to support the efficacy of this methodology for the incorporation of neutral species within conducting polymer films.     

Alterations in osmoregulation, antioxidant enzymes and indole alkaloid levels in Catharanthus roseus exposed to water deficit

Catharanthus roseus (L.) G. Don plants were grown in different water regimes in order to study the drought induced osmotic stress and proline (PRO) metabolism, antioxidative enzyme activities and indole alkaloid accumulation. The plants under pot culture were subjected to 10, 15 and 20 days interval drought (DID) stress from 30 days after sowing (DAS) and regular irrigation was kept as control. The plants were uprooted on 41 DAS (10 DID), 46 DAS (15 DID) and 51 DAS (20 DID). The drought stressed plants showed increased aminoacid (AA), glycine betaine (GB) and PRO contents and decreased proline oxidase (PROX) and increased γ-glutamyl kinase (γ-GK) activities when compared to control. The antioxidative enzymes like peroxidase (POX) and polyphenol oxidase (PPO) increased to a significant level in drought stressed plants when compared to control. The drought stressed C. roseus plants showed an increase in total indole alkaloid content in shoots and roots when compared to well-watered control plants. Our results suggest that the cultivation of medicinal plants like C. roseus in water deficit areas would increase its PRO metabolism, osmoregulation, defense system and the level of active principles.     

Synthesis, characterization and antimicrobial investigation of mechanochemically processed silver doped ZnO nanoparticles

The application of nanomaterials has gained considerable momentum in various fields in recent years due to their high reactivity, excellent surface properties and quantum effects in the nanometer range. The properties of zinc oxide (ZnO) vary with its crystallite size or particle size and often nanocrystalline ZnO is seen to exhibit superior physical and chemical properties due to their higher surface area and modified electronic structure. ZnO nanoparticles are reported to exhibit strong bacterial inhibiting activity and silver (Ag) has been extensively used for its antimicrobial properties since ages. In this study, Ag doped ZnO nanoparticles were synthesized by mechanochemical processing in a high energy ball mill and investigated for antimicrobial activity. The nanocrystalline nature of zinc oxide was established by X-ray diffraction (XRD) studies. It is seen from the XRD data obtained from the samples, that crystallite size of the zinc oxide nanoparticles is seen to decrease with increasing Ag addition. Field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) data also supported the nanoparticle formation during the synthesis. The doped nanoparticles were subjected to antimicrobial investigation and found that both increase in Ag content and decrease in particle size contributed significantly towards antimicrobial efficiency. It was also observed that Ag doped ZnO nanoparticles possess enhanced antimicrobial potential than that of virgin ZnO against the studied microorganisms of Escherichia coli and Staphylococcus aureus.     

Evaluation of bias voltage effect on diamond‐like carbon coating properties deposited on tungsten carbide cobalt

Diamond‐like carbon (DLC) coatings are getting new trends for cutting tool applications. In this research work, the DLC coatings were deposited on 15 × 15 × 5‐mm tungsten carbide cobalt substrates with variation of bias voltage from 0 to 500 V. The DLC films of 400 nm were deposited using filter cathode vacuum arc system, and 100‐nm chromium interlayer was deposited by sputtering. The optimized conditions for plasma pretreatment at different argon flow rates and deposition rates with bias variation were found. The effect of bias voltage on microstructure, tribology, adhesion, and mechanical properties were evaluated. The characterization techniques employed were field emission electron microscopy, Raman spectroscopy, wear test, SEM, scratch test, and nano‐indentation. The effect of substrate pretreatment on film adhesion was also evaluated. It was observed that etching rate increased with the increase in Ar flow rate while DLC deposition and sputtering rates decreased with increase in the bias voltage. The characterization suggests the DLC coatings deposited at 0 V bias as optimum condition because of showing the best results among all other conditions. Copyright © 2014 John Wiley & Sons, Ltd.     

Effect of Temperature on Cd2+ Sorption by Mixed Oxides of Iron and Silicon

The current study focuses on the synthesis and sorption properties of two mixed oxides of iron and silicon prepared by physical mixing (M₁) and sequential precipitation methods (M₂). Both the mixed oxides were synthesized from equimolar ratios of Fe(OH)₃ and SiO₂ and characterized for surface area, EDX, XRD and PZC. The surface area, micropore volume and average pore width of the oxide M₁ were higher as compared to the oxide M₂. However, potentiometric titrations revealed that mixed oxide synthesized by this method had a very high capacity towards Cd²⁺ ions as compared to the mixed oxide M₁. Sorption of Cd²⁺ ions at pH 5 on mixed oxide, M₂ was found to increase with temperature in the range 288 to 318 K. Langmuir equation was found applicable to the sorption data with R²>0.99. Entropy (ΔS^?), enthalpy (ΔH^?) and free energy changes (ΔG^?) were calculated which revealed the process to be endothermic and spontaneous in nature.     

Platform for Highly Sensitive Alkaline Phosphatase‐Based Immunosensors Using 1‐Naphthyl Phosphate and an Avidin‐Modified Indium Tin Oxide Electrode

We report a versatile platform for highly sensitive alkaline phosphatase (ALP)‐based electrochemical biosensors that uses an avidin‐modified indium tin oxide (ITO) electrode as a sensing electrode and 1‐naphthyl phosphate (NPP) as an ALP substrate. Almost no electrocatalytic activity of NPP and good electrocatalytic activity of 1‐naphthol (ALP product) on the ITO electrodes allow a high signal‐to‐background ratio. The effective surface covering of avidin on the ITO electrodes allows very low levels of nonspecific binding of proteins to the sensing electrodes. The platform technology is used to detect mouse IgG with a detection limit of 1.0 pg/mL.