Structural, optical and EPR studies on ZnO:Cu nanopowders prepared via low temperature solution combustion synthesis

Cu (0.1 mol%) doped ZnO nanopowders have been successfully synthesized by a wet chemical method at a relatively low temperature (300 degrees C). Powder X-ray diffraction (PXRD) analysis, scanning electron microscopy (SEM), Transmission electron microscopy (TEM), Fourier transformed infrared (FTIR) spectroscopy, UV-Visible spectroscopy, Photoluminescence (PL) and Electron Paramagnetic Resonance (EPR) measurements were used for characterization. PXRD results confirm that the nanopowders exhibit hexagonal wurtzite structure of ZnO without any secondary phase. The particle size of as-formed product has been calculated by Williamson-Hall (W-H) plots and Scherrer's formula is found to be in the range of similar to 40 nm. TEM image confirms the nano size crystalline nature of Cu doped ZnO. SEM micrographs of undoped and Cu doped ZnO show highly porous with large voids. UV-Vis spectrum showed a red shift in the absorption edge in Cu doped ZnO. PL spectra show prominent peaks corresponding to near band edge UV emission and defect related green emission in the visible region at room temperature and their possible mechanisms have been discussed. The EPR spectrum exhibits a broad resonance signal at g similar to 2.049, and two narrow resonances one at g similar to 1.990 and other at g similar to 1.950. The broad resonance signal at g similar to 2.049 is a characteristic of Cu2+ ion whereas the signal at g similar to 1.990 and g similar to 1.950 can be attributed to ionized oxygen vacancies and shallow donors respectively. The spin concentration (N) and paramagnetic susceptibility (X) have been evaluated and discussed. (C) 2011 Elsevier B. V. All rights reserved.

Synthesis and characterization of poly(vinyl acetate peroxide)

Poly(vinyl acetate peroxide) (PVACP) was prepared from vinyl acetate by free-radical-initiated oxidative polymerization. The polyperoxide was isolated and characterized by different spectroscopic methods. The extreme instability of PVACP was demonstrated by FTIR spectroscopy. The H-1- and C-13-NMR studies show the irregularities in the polyperoxide chain due to the cleavage reactions of the propagating peroxide radical. Thermal degradation studies using differential scanning calorimetry revealed that PVACP degrades at a lower temperature and the heat of degradation is in the same range as reported for other vinyl polyperoxides. (C) 1996 John Wiley & Sons, Inc.

A study of Al2O3:C films on Si(100) grown by low pressure MOCVD

We report the characterization of carbonaceous aluminium oxide, Al2O3:C, films grown on Si(100) by metalorganic chemical vapor deposition. The focus is on the study of the effects of carbon on the dielectric properties of aluminium oxide in a qualitative manner. The carbon present in the aluminium oxide film derives from aluminium acetylacetonate used as the source of aluminium. As-grown films comprise nanometer-sized grains of alumina (∼ 20–50 nm) in an amorphous carbonaceous matrix, as examined by X-ray diffractometry (XRD) and transmission electron microscopy (TEM). The films are shiny; they are smooth as observed by scanning electron microscopy (SEM). An attempt has been made to explore the defects (viz., oxide charge density) in the aluminium oxide films using room temperature high frequency capacitance – voltage (C-V) and current–voltage (I-V) measurements. The hysteresis and stretch-out in the high frequency C-V plots is indicative of charge trapping. The role of heteroatoms, as characterized by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy, in the transport of charge in Al2O3:C films is discussed.

Surfactant-mediated Synthesis of Functional Metal Oxide Nanostructures via Microwave Irradiation-assisted Chemical Synthesis

Nanostructured materials have attracted considerable interest in recent years due to their properties which differ strongly from their bulk phase and potential applications in nanoscale electronic and optoelectronic devices. Metal oxide nanostructures can be synthesized by variety of different synthesis techniques developed in recent years such as thermal decomposition, sol-gel technique, chemical coprecipitation, hydrothermal process, solvothermal process, spray pyrolysis, polyol process etc. All the above processes go through a tedious synthesis procedure followed by prolonged heat treatment at elevated temperature and are time consuming. In the present work we describe a rapid microwave irradiation-assisted chemical synthesis technique for the growth of nanoparticles, nanorods, and nanotubes of a variety of metal oxides in the presence of an appropriate surfactant, without the use of any templates The method is simple, inexpensive, and helps one to prepare nanostructures in a very simple way, and in a very short time, measured in minutes. The synthesis procedure employs high quality metalorganic complexes (typically -diketonates) featuring a direct metal-to-oxygen bond in its molecular structure. The complex is dissolved in a suitable solvent, often with a surfactant added, and the solution then subjected to microwave irradiation in a domestic microwave oven operating at 2.45 GHz frequency with power varying from 160-800 W, from a few seconds to a few minutes, leading to the formation of corresponding metal oxides. This method has been used successfully to synthesize nanostructures of a variety of binary and ternary metal oxides such as ZnO, CdO, Fe2O3, CuO, Ga2O3, Gd2O3, ZnFe2O4, etc. There is an observed variation in the morphology of the nanostructures with the change of different parameters such as microwave power, irradiation time, appropriate solvent, surfactant type and concentration. Cationic, anionic, nonionic and polymeric surfactants have been used to generate a variety of nanostructures. Even so, to remove the surfactant, there is either no need of heat treatment or a very brief exposure to heat suffices, to yield highly pure and crystalline oxide materials as prepared. By adducting the metal complexes, the shape of the nanostructures can be controlled further. In this manner, very well formed, single-crystalline, hexagonal nanorods and nanotubes of ZnO have been formed. Adducting the zinc complex leads to the formation of tapered ZnO nanorods with a very fine tip, suitable for electron emission applications. Particle size and their monodispersity can be controlled by a suitable choice of a precursor complex, the surfactant, and its concentration. The resulting metal oxide nanostructures have been characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, FTIR spectroscopy, photoluminescence, and electron emission measurements.

Lubricity of an oil in water emulsion in metal cutting: The effect of hydrophilic/lypophilic balance of emulsifiers

A steel disc is cut using a single point tool. The coefficient of friction of the nascent cut surface is measured by a spherical steel pin situated in close proximity of the point of cutting. The tool, disc and the friction pin are immersed in an oil in water emulsion bath during the experiment. The purpose of the experiments conducted here is to record the effect of hydrophilic/lypophilic balance (HLB) of the emulsifier on the lubricity experienced in the cutting operation. The more lypophilic emulsifiers were found to give greater lubricity than what is recorded when the emulsifier is more hydrophilic. XPS and FTIR spectroscopy are used to explore the tribofilm generated on the nascent cut surface to indicate a possible rationale for the effect. (C) 2011 Elsevier B.V. All rights reserved.

Synthesis of nanocomposites of Ni-Zn ferrite in aniline formaldehyde copolymer and studies on their pyrolysis products

Synthesis of nanoparticles of Ni-Zn ferrite dispersed in aniline formaldehyde copolymer using a room temperature route and the effect of heat treatment on these samples were studied using XRD, FTIR spectroscopy, Fe-57 Mossbauer spectroscopy and TEM microscopy. The results show the formation of nanosized particles of Ni-Zn ferrite in the polymer matrix at room temperature. On pyrolysis, the Ni-Zn ferrite phase persists up to 500 degreesC. However, heating of composites to 700 degreesC results in the partial reduction of the spinet ferrite leading to the formation of Ni-Fe alloy under ambient conditions and complete reduction of the alloy on heating in inert atmosphere. (C) 2003 Elsevier B.V. All rights reserved.

Biodegradation of some organic reagents from mineral process effluents

The utility of a soil microbe, namely Bacillus polymyxa, in the removal of organic reagents such as dodecylamine, ether diamine, isopropyl xanthate and sodium oleate from aqueous solutions is demonstrated. Time-bound removal of the above organic reagents from an alkaline solution was investigated under different experimental conditions during bacterial growth and in the presence of metabolites by frequent monitoring of residual concentrations as a function of time, reagent concentration and cell density. The stages and mechanisms in the biodegradation process were monitored through UV-visible and FTIR spectroscopy. Surface chemistry of the bacterial cells as well as the biosorption tendency for various organics were also established through electrokinetic and adsorption density measurements. Both the cationic amines were found to be biosorbed followed by their degradation through bacterial metabolism. The presence of the organic reagents promoted bacterial growth through effective bacterial utilization of nitrogen and carbon from the organics. Under optimal conditions, complete degradation and bioremoval of all the organics could be achieved.

One step synthesis of monoclinic VO2 (B) bundles of nanorods: Cathode for Li ion battery

One of the metastable phases of vanadium dioxide, VO2(B) bundles of nanorods and microspheres have been synthesized through a simple hydrothermal method by dispersing V2O5 in aqueous quinol. The obtained products were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and electrochemical discharge-charge test for lithium battery. It was found that the morphologies of the obtained VO2(B) can be tuned by manipulating the relative amount of quinol. The electrochemical test found that the bundles of nanorods exhibit an initial discharge capacity of 171 mAh g(-1) and its almost stabilized capacity was reached to 108 mAh g(-1) after 47 cycles at a current density of 0.1 mA g(-1). The formation mechanism of the VO2(B) bundles of nanorods and microspheres was also discussed. (C) 2012 Elsevier Inc. All rights reserved.

Infrared Spectroscopic Studies to Understand the Effect of Drugs at Molecular Level

In the recent past, there have been enormous efforts to understand effect of drugs on human body. Prior to understand the effect of drugs on human body most of the experiments are carried out on cells or model organisms. Here we present our study on the effect of chemotherapeutic drugs on cancer cells and the acetaminophen (APAP) induced hepatotoxicity in mouse model. Histone deacetylase inhibitors (HDIs) have attracted attention as potential drug molecules for the treatment of cancer. These are the chemotherapeutic drugs which have indirect mechanistic action against cancer cells via acting against histone deacetylases (HDAC). It has been known that different HDAC enzymes are over-expressed in various types of cancers for example; HDAC1 is over expressed in prostate, gastric and breast carcinomas. Therefore, in order to optimise chemotherapy, it is important to determine the efficacy of various classes of HDAC inhibitor drugs against variety of over-expressed HDAC enzymes. In the present study, FTIR microspectroscopy has been employed to predict the acetylation and propionylation brought in by HDIs. The liver plays an important role in cellular metabolism and is highly susceptible to drug toxicity. APAP which is an analgesic and antipyretic drug is extensively used for therapeutic purposes and has become the most common cause of acute liver failure (ALF). In the current study, we have focused to understand APAP induced hepatotoxicity using FTIR microspectroscopy. In the IR spectrum the bands corresponding to glycogen, ester group and were found to be suitable markers to predict liver injury at early time point (0.5hr) due to APAP both in tissue and serum in comparison to standard biochemical assays. Our studies show the potential of FTIR spectroscopy as a rapid, sensitive and non invasive detection technique for future clinical diagnosis.

The irradiation of 1:1 mixture of ammonia:carbon dioxide ice at 30 K using 1 kev electrons

In this Letter the results of an experimental investigation of 1 keV electron irradiation of a 1:1 ice mixture of NH3:CO2 at 30 K was made under ultrahigh vacuum (10(-9) mbar) conditions. Molecular products formed within the ice were detected and monitored using FTIR spectroscopy. The formation of ammonium ions (NH4+), cyanate ions (OCN-), CO was observed leading to the synthesis of ammonium carbamate (NH4NH2CO2). The consequences of these results for prebiotic chemistry in the interstellar medium and star forming regions are discussed. Crown Copyright (C) 2012 Published by Elsevier B.V. All rights reserved.

Substrate integrated Lead-Carbon hybrid ultracapacitor with flooded, absorbent glass mat and silica-gel electrolyte configurations

Lead-Carbon hybrid ultracapacitors (Pb-C HUCs) with flooded, absorbent-glass-mat (AGM) and silica-gel sulphuric acid electrolyte configurations are developed and performance tested. Pb-C HUCs comprise substrate-integrated PbO2 (SI-PbO2) as positive electrodes and high surface-area carbon with graphite-sheet substrate as negative electrodes. The electrode and silica-gel electrolyte materials are characterized by XRD, XPS, SEM, TEM, Rheometry, BET surface area, and FTIR spectroscopy in conjunction with electrochemistry. Electrochemical performance of SI-PbO2 and carbon electrodes is studied using cyclic voltammetry with constant-current charge and discharge techniques by assembling symmetric electrical-double-layer capacitors and hybrid Pb-C HUCs with a dynamic Pb(porous)/PbSO4 reference electrode. The specific capacitance values for 2 V Pb-C HUCs are found to be 166 F/g, 102 F/g and 152 F/g with a faradaic efficiency of 98%, 92% and 88% for flooded, AGM and gel configurations, respectively.

The irradiation of pure CH3OH and 1:1 mixture of NH3:CH3OH ices at 30 K using low energy electrons

The results of an experimental investigation of 1 keV electron irradiation of ices (deposited at 30 K) of (i) pure methanol and (ii) of a 1:1 mixture of NH3:CH3OH are reported. Molecular products formed within the ice were detected and monitored using FTIR spectroscopy. The products observed were methyl formate (H3COHCO), methane (CH4), hydroxymethyl (CH2OH), formamide (HCONH2), formic acid (HCOOH), formaldehyde (H2CO), formyl radical (HCO), cyanate ion (OCN-), isocyanic acid (HNCO), carbon monoxide (CO) and carbon dioxide (CO2). The consequences of these results for prebiotic chemistry in the interstellar medium and star forming regions are discussed. Crown Copyright (C) 2012 Published by Elsevier B. V. All rights reserved.

Steric and Electronic Interactions Controlling the cis/trans Isomer Equilibrium at X-Pro Tertiary Amide Motifs in Solution

A systematic understanding of the noncovalent interactions that influence the structures of the cis conformers and the equilibrium between the cis and the trans conformers, of the X-Pro tertiary amide motifs, is presented based on analyses of H-1-, C-13-NMR and FTIR absorption spectra of two sets of homologous peptides, X-Pro-Aib-OMe and X-Pro-NH-Me (where X is acetyl, propionyl, isobutyryl and pivaloyl), in solvents of varying polarities. First, this work shows that the cis conformers of any X-Pro tertiary amide motif, including Piv-Pro, are accessible in the new motifs X-Pro-Aib-OMe, in solution. These conformers are uniquely observable by FTIR spectroscopy at ambient temperatures and by NMR spectroscopy from temperatures as high as 273 K. This is made possible by the persistent presence of n(i-1i)* interactions at Aib, which also influence the disappearance of steric effects at these cis X-Pro rotamers. Second, contrary to conventional understanding, the energy contribution of steric effects to the cis/trans equilibrium at the X-Pro motifs is found to be nonvariant (0.54 +/- 0.02 kcal/mol) with increase in steric bulk on the X group. Third, the current studies provide direct evidence for the weak intramolecular interactions namely the n(i-1i)*, the N-Pro center dot center dot center dot Hi+1 (C(5)a), and the C-7 hydrogen bond that operate and influence the structures, stabilities, and dynamics between different conformational states of X-Pro tertiary amide motifs. NMR and IR spectral data suggest that the cis conformers of X-Pro motifs are ensembles of short-lived rotamers about the C-X-N-Pro bond. (c) 2013 Wiley Periodicals, Inc. Biopolymers 101: 66-77, 2014.

Remarkable Regioisomer Control in the Hydrogel Formation from a Two-Component Mixture of Pyridine-End Oligo(p-phenylenevinylene)s and N-Decanoyl-L-alanine

N-Decanoyl-L-alanine (DA) was mixed with either colorless 4,4-bipyridine (BP) or various derivatives such as chromogenic oligo(p-phenylenevinylene) (OPV) functionalized with isomeric pyridine termini in specific molar ratios. This mixtures form salt-type gels in a water/ethanol (2:1, v/v) mixture. The gelation properties of these two-component mixtures could be modulated by variation of the position of the N atom of the end pyridyl groups in OPVs. The presence of acid-base interactions in the self-assembly of these two-component systems leading to gelation was probed in detail by using stoichiometry-dependent UV/Vis and FTIR spectroscopy. Furthermore, temperature-dependent UV/Vis and fluorescence spectroscopy clearly demonstrated a J-type aggregation mode of these gelator molecules during the sol-to-gel transition process. Morphological features and the arrangement of the molecules in the gels were examined by using scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray diffraction (XRD) techniques. Calculation of the length of each molecular system by energy minimization in its extended conformation and comparison with the XRD patterns revealed that this class of gelator molecules adopts lamellar organizations. Rheological properties of these two-component systems provided clear evidence that the flow behavior could be modulated by varying the acid/amine ratio. Polarized optical microscopy (POM), differential scanning calorimetry (DSC), and XRD results revealed that the solid-phase behavior of such two-component mixtures (acid/base=2:1) varied significantly upon changing the proton-acceptor part from BP to OPV. Interestingly, the XRD pattern of these acid/base mixtures after annealing at their associated isotropic temperature was significantly different from that of their xerogels.

A promising ketone containing alternating copolymer for organic photovoltaics

An alternating copolymer containing dithienylcyclopentadienone, thiophene and benzothiadiazole was synthesized by palladium (0) catalyzed Stille coupling reaction. Structural characterization of the synthesized alternating copolymer was carried out by NMR and FTIR spectroscopy. This solution processable copolymer shows an excellent thermal stability and has a broad absorption range from 300-800 nm. High LUMO energy level and low band gap of the synthesized copolymers suggest that, this copolymer will be a better donor material for application in organic photovoltaics. Particle size analysis and molecular weight determination of the synthesized copolymer through dynamic light scattering experiment indicates that, high molecular weight copolymer was obtained by this polymerization route. Photovoltaic devices were fabricated from the blend of copolymer and phenyl-C61- butyric acid methyl ester as the active material. Fabricated photovoltaic device results show that this alternating copolymer is a promising candidate for use in organic photovoltaics.