Volume 65, Issue 4
October 2005, pages 547-768
pp 547-548 October 2005
pp 549-564 October 2005
Soft chemistry has emerged as an important means of generating nanocrystals, nanowires and other nanostructures of semiconducting materials. We describe the synthesis of CdS and other metal chalcogenide nanocrystals by a solvothermal route. We also describe the synthesis of nanocrystals of AlN, GaN and InN by the reaction of hexamethyldisilazane with the corresponding metal chloride or metal cupferronate under solvothermal conditions. Nanowires of Se and Te have been obtained by a self-seeding solution-based method. A single source precursor based on urea complexes of metal chlorides gives rise to metal nitride nanocrystals, nanowires and nanotubes. The liquidliquid interface provides an excellent medium for preparing single-crystalline films of metal chalcogenides.
pp 565-570 October 2005
We report an easy, one pot synthesis to prepare ordered CdS nanocrystals with varying inter-particle separation and characterize the particle separation using x-ray diffraction at low and wide angles.
pp 571-579 October 2005
The flow of various liquids and gases over single-walled carbon nanotube bundles induces an electrical signal (voltage/current) in the sample along the direction of the flow. The electrical response generated by the flow of liquids is found to be logarithmic in the flow speed over a wide range. In contrast, voltage generated by the flow of gas is quadratically dependent on the gas flow velocity. It was found that the underlying physics for the generation of electrical signals by liquids and gases are different. For the liquid, the Coulombic interaction between the ions in the liquid and the charge carriers in the nanotube plays a key role while electrical signal generation due to gas flow is due to an interplay of Bernoulli’s principle and Seebeck effect. Unlike the liquid case which is specific to the nanotubes, the gas flow effect can be seen for a variety of solids ranging from single and multi-walled carbon nanotubes, graphite and doped semiconductors.
pp 581-592 October 2005
TiO2 nanostructured films have been synthesized by the hydrolysis of Ti[OCH(CH3)2]4 as the precursor. These films have been utilized for the dissociation of phenol contaminant in water. Free-standing nanostructured film of silicon carbide (SiC) has been synthesized, employing a simple and new route of spray pyrolysis technique utilizing a slurry of Si in hexane. Another study is done on organized carbon nanotube (CNT) structures. These are made in the form of hollow cylinders (50 mm length, 4 mm diameter and 1.5 mm wall thickness). These CNT-based cylinders are made of conventional CNT and bamboo-shaped CNT. The filtrations of heavy hydrocarbons andE. coli bacteria from water have been carried out. In addition to this, ZnO nanostructures have also been studied. Another study concerns CNT-blood platelet clusters.
pp 593-599 October 2005
We have investigated the effects of electron-phonon coupling on the current-voltage characteristics of a one-dimensional molecular wire with odd number of atoms. The wire has been modelled using the Su-Schreiffer-Heeger (SSH) Hamiltonian and the current-voltage characteristics have been obtained using the Landauer’s formalism. In the presence of strong electron-lattice coupling, we find that there are regions of negative differential resistance (NDR) at some critical bias, due to the degeneracy in the energies of the frontier molecular orbitals. The presence of the applied bias and the electron-lattice coupling results in the delocalization of these low-lying molecular states leading to the NDR behaviour.
pp 601-614 October 2005
We present a mini-review of our recent work on spontaneous, self-organized creation of mesostructures in soft materials like thin films of polymeric liquids and elastic solids. These very small scale, highly confined systems are inherently unstable and thus self-organize into ordered structures which can be exploited for MEMS, sensors, opto-electronic devices and a host of other nanotechnology applications. In particular, mesomechanics requires incorporation of intermolecular interactions and surface tension forces, which are usually inconsequential in classical macroscale mechanics. We point to some experiments and quasi-continuum simulations of self-organized structures in thin soft films which are germane not only to nanotechnology, but also to a spectrum of classical issues such as adhesion/debonding, wetting, coatings, tribology and membranes.
pp 615-620 October 2005
Zinc oxide and cadmium selenide particles in the nanometer size regime have been synthesized using chemical routes. The particles were capped using thioglycerol in case of ZnO and 2-mercaptoethanol in case of CdSe to achieve the stability and avoid the coalescence. Zinc oxide nanoparticles were doped with europium to study their optical properties. A variety of techniques like UV-Vis absorption spectroscopy, X-ray diffraction (XRD), photoluminescence (PL), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR) and transmission electron microscopy (TEM) were used to carry out structural and spectroscopic characterizations of the nanoparticles.
pp 621-630 October 2005
In this paper we report a new method of fabrication of surface tensionconfined microfluidic devices on glass. We have also successfully carried out some well-known chemical reactions in these fluidic channels to demonstrate the usefulness of these wall-less microchannels. The confined flow path of liquid was achieved on the basis of extreme differences in hydrophobic and hydrophilic characters of the surface. The flow paths were fabricated by making parallel lines using permanent marker pen ink or other polymer on glass surfaces. Two mirror image patterned glass plates were then sandwiched one on top of the other, separated by a thin gap-created using a spacer. The aqueous liquid moves between the surfaces by capillary forces, confined to the hydrophilic areas without wetting the hydrophobic lines, achieving liquid confinement without physical side-walls. We have shown that the microfluidic devices designed in such a way can be very useful due to their simplicity and low fabrication cost. More importantly, we have also demonstrated that the minimum requirement of such a working device is a hydrophilic line surrounded by hydrophobic environment, two walls of which are constituted of air and the rest is made of a hydrophobic surface.
pp 631-640 October 2005
In this paper, an overview of the synthesis, chemistry and applications of nanosystems carried out in our laboratory is presented. The discussion is divided into four sections, namely (a) chemistry of nanoparticles, (b) development of new synthetic approaches, (c) gas phase clusters and (d) device structures and applications. In ‘chemistry of nanoparticles’ we describe a novel reaction between nanoparticles of Ag and Au with halocarbons. The reactions lead to the formation of various carbonaceous materials and metal halides. In ‘development of new synthetic approaches’ our one-pot methodologies for the synthesis of core-shell nanosystems of Au, Ag and Cu protected with TiO2 and ZrO2 as well as various polymers are discussed. Some results on the interaction of nanoparticles with biomolecules are also detailed in this section. The third section covers the formation of gas phase aggregates/clusters of thiol-protected sub-nanoparticles. Laser desorption of H2MoO4, H2WO4, MoS2, and WS2 giving novel clusters is discussed. The fourth section deals with the development of simple devices and technologies using nanomaterials described above.
pp 641-645 October 2005
We have synthesized 5–7 nm size, highly crystalline TiO2 which absorbs radiation in the visible region of solar spectrum. The material shows higher photocatalytic activity both in UV and visible region of the solar radiation compared to commercial Degussa P25 TiO2. Transition metal ion substitution for Ti4+ creates mid-gap states which act as recombination centers for electron-hole induced by photons thus reducing photocatalytic activity. However, Pt, Pd and Cu ion substituted TiO2 are excellent CO oxidation and NO reduction catalysts at temperatures less than 100° C.
pp 647-652 October 2005
The dispersal of CuO catalyst on the surface of the semiconducting SnO2 film is found to be of vital importance for improving the sensitivity and the response speed of a SnO2 gas sensor for H2S gas detection. Ultra-thin CuO islands (8 nm thin and 0.6 mm diameter) prepared by evaporating Cu through a mesh and subsequent oxidation yield a fast response speed and recovery. Ultimately nanoparticles of Cu (average size = 15 nm) prepared by a chemical technique using a reverse micelle method involving the reduction of Cu(NO3)2 by NaBH4 exhibited significant improvement in the gas sensing characteristics of SnO2 films. A fast response speed of ∼14 s and a recovery time of ∼60 s for trace level ∼20 ppm H2S gas detection have been recorded. The sensor operating temperature (130° C) is low and the sensitivity (S = 2.06 × 103) is high. It is found that the spreading over of CuO catalyst in the nanoscale range on the surface of SnO2 allows effective removal of excess adsorbed oxygen from the uncovered SnO2 surface due to spill over of hydrogen dissociated from the H2S-CuO interaction.
pp 653-661 October 2005
We have measured the permeability of rhodamine-6G across Cx43 hemichannels reconstituted on a pipette tip. Cx43 hemichannels were overexpressed in Sf9 cells, and affinity-purified. The hemichannels were reconstituted in a lipid bilayer on a pipette tip by the tip-dip method. R6G in the pipette permeated across the channels into the bath. The permeability of R6G was quantified by measuring R6G concentration in the bath after several hours by surface enhanced Raman spectroscopy (SERS) with 100 nm silver colloid particles. The ratio of the permeability of dye to salt, as extracted by this combined electrical-SERS technique, is compatible with similar ratios for other dyes across whole gap junction channels. The results for the permeability ratio were further compared to fluorescence measurements. The novel combination of patch and SERS techniques can be extended to quantifying the transport of biologically significant non-fluorescent molecules, such as cAMP and IP3, across 1 nm sized pores, such as the gap junction channel.
pp 663-679 October 2005
Magnetic nanoparticles have been prepared by various soft chemical methods including self-assembly. The bare or surface-modified particles find applications in areas such as hyperthermia treatment of cancer and magnetic field-assisted radioactive chemical separation. We present here some of the salient features of processing of nanostructured magnetic materials of different sizes and shapes, their properties and some possible applications. The materials studied included metals, metal-ceramic composites, and ferrites.
pp 681-697 October 2005
Carbon nanotubes (CNT) has been synthesized by pyrolysing mustard oil using an oil lamp. It was made water-soluble (wsCNT) through oxidative treatment by dilute nitric acid and was characterized by SEM, AFM, XRD, Raman and FTIR spectroscopy. The synthesized wsCNT showed the presence of several junctions and defects in it. The presence of curved graphene structure (sp2) with frequent sp3 hybridized carbon is found to be responsible for the observed defects. These defects along with the presence of di- and tri-podal junctions showed interesting magnetic properties of carbon radicals formed by spin frustration. This trapped carbon radical showed ESR signal in aqueous solution and was very stable even under drastic treatment by strong oxidizing or reducing agents. Oxidative acid treatment of CNT introduced several carboxylic acid group functionalities in wsCNT along with the nicking of the CNT at different lengths with varied molecular weight. To evaluate molecular weights of these wsCNTs, an innovative method like gel electrophoresis using high molecular weight DNA as marker was introduced.
pp 699-705 October 2005
The optical tweezer is a versatile set-up that can be employed in a wide variety of studies investigating the microscopic properties of materials. In particular, this set-up has in recent times been gainfully employed in probing rheological properties of materials that exhibit viscoelasticity. These measurements can provide data at the micro and nanometer scales, not normally accessible by rheometers that are used for measurements on bulk samples. In this work we describe a single laser beam optical tweezer set-up, which is built around an inverted open microscope. The trapped polystyrene particle bead’s deviation from the trap potential minimum is monitored by laser backscattering technique and the bead position measured by a quadrant photodiode detector. Additionally, a provision is made for video microscopic studies on dispersed beads using a CCD camera. A single particle microrheological experiment that can be performed using the set-up is described with relevant calculations.
pp 707-712 October 2005
The present work describes the synthesis of CdS/CdSSe glass nanocomposites and its characterization. A few glass compositions were optimized and the optimized host glass was remelted along with different semiconductors like CdS and CdSSe at high temperature. The CdS/CdSSe is present in amorphous state in the glass matrix. The thermal treatments have been carefully optimized to obtain well-defined uniform crystal growth of CdS and CdSSe. The glasses with optimized conditions were fabricated and characterized thoroughly using UV, TG/DTA and TEM. The shift in absorption edge to the longer wavelength with heat treatment implies the increase in the crystal size. The band gap has been increased with decrease in the particle size. Crystal size of semiconductors obtained by TEM was 2.5-5 nm for the glass showing absorption edge cut-off at 475 nm (CM-475).
pp 713-722 October 2005
The electrocatalytic activity of nanostructured copper particles (represented as Cunano) incorporated Nafion (Nf) film-coated glassy carbon (GC) electrode (GC/Nf/Cunano) towards oxygen reduction was investigated in oxygenated 0.1 M phosphate buffer (pH 7.2). The electrodeposited Cunano in Nf film was characterized by atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The electrocatalytic activity of Cunano at the modified electrode towards oxygen reduction was studied using cyclic voltammetry technique. The molecular oxygen reduction at the GC/Nf/Cunano-modified electrode started at a more positive potential than at a bare GC electrode. A possible reaction mechanism was proposed in which oxygen reduction may proceed through two-step two-electron processes at the GC/Nf/Cunano electrode. The GC/Nf/Cunano electrode shows higher stability for oxygen reduction in neutral solution and the electrode may find applications in fuel cells.
pp 723-729 October 2005
Viral and nonviral condensing agents are used in gene therapy to compact oligonucleotides and plasmid DNA into nanostructures for their efficient transport through the cell membranes. Whereas viral vectors are best by the toxic effects on the immune system, most of the nonviral delivery vehicles are not effective for use in clinical system. Recent investigations indicate that the supramolecular organization of DNA in the condensed state is liquid crystalline. The present level of understanding of the liquid crystalline phase of DNA is inadequate and a thorough investigation is required to understand the nature, stability, texture and the influence of various environmental conditions on the structure of the phase. The present study is mainly concerned with the physicochemical investigations on the liquid crystalline transitions during compaction of DNA by cationic species such as polyamines and metallic cations. As a preliminary to the above investigation, studies were conducted on the evolution of mesophase transitions of DNA with various cationic counterion species using polarized light microscopy. These studies indicated significant variations in the phase behaviour of DNA in the presence of Li and other ions. Apart from the neutralization of the charges on the DNA molecule, these ions are found to influence selectively the hydration sphere of DNA that in turn influences the induction and stabilization of the LC phases. The higher stability observed with the liquid crystalline phases of Li-DNA system could be useful in the production of nanostructured DNA. In the case of the polyamine, a structural specificity effect depending on the nature, charge and structure of the polyamine used has been found to be favoured in the crystallization of DNA.
pp 731-738 October 2005
Chemical functionalization of single-walled carbon nanotubes with redox mediators, namely, toluidine blue and thionin have been carried out and the performance of graphite electrode modified with functionalized carbon nanotubes is described. Mechanical immobilization of functionalized single-walled nanotube (SWNT) on graphite electrode was achieved by gently rubbing the electrode surface on carbon nanotubes supported on a glass slide. The electrochemical behaviour of the modified electrodes was investigated by cyclic voltammetry. The SWNT-modified electrodes showed excellent electrocatalytic effect for the reduction of hydrogen peroxide. A decrease in overvoltage was observed as well as an enhanced peak current compared to a bare graphite electrode for the reduction of hydrogen peroxide. The catalytic current was found to be directly proportional to the amount of hydrogen peroxide taken.
pp 739-743 October 2005
The interaction effects in magnetic nanoparticle system were studied through a Monte Carlo simulation. The results of simulations were compared with two different magnetic systems, namely, iron oxide polymer nanocomposites prepared by polymerization over core and nanocrystalline cobalt ferrite thin films prepared by sol-gel process. The size of the particles in the nanocomposites were estimated to be ∼15 nm with very little agglomeration. The low values of the coercivity obtained from the hysteresis measurements performed confirm that the system is superparamagnetic. SEM studies showed the cobalt ferrite films to have a nanocrystalline character, with particle sizes in the nanometer range. Hysteresis measurements performed on the thin films coated on silicon do not give evidence of the superparamagnetic transition up to room temperature and the coercivity is found to increase with decreasing film thickness. Comparison with simulations indicate that the nanocomposites behave like a strongly interacting array where exchange interactions lead to high blocking temperatures, whereas the films are representative of a semi-infinite array of magnetic clusters with weak interactions and thickness-dependent magnetic properties.
pp 745-751 October 2005
The crystallization behaviour and evolution of nanoparticles in amorphous Al-Ni-Mischmetal (Mm) and Al-Ni-La alloys during heat treatment have been studied. Rapidly solidified ribbons were obtained by induction melting and ejecting the melt onto a rotating Cu wheel in an Ar atmosphere.
The crystallization behaviour of the melt-spun ribbons was investigated using differential scanning calorimetry and X-ray diffractometry (XRD). XRD studies confirmed that all the ribbons were fully amorphous. Al-Ni-Mm systems showed a three-stage crystallization process whereas Al-Ni-La system, in general, showed a two-stage crystallization process on annealing. Crystallization kinetics was analysed by Kissinger and Johnson-Mehl-Avrami approaches. In Al-Ni-La alloys, the crystallization pathways depend on the La concentration. Microhardness of all the ribbons was examined at different temperatures and correlated with the corresponding evolution of phases.
pp 753-761 October 2005
The effect of chain length on the adhesion behaviour of n-alkanethiols CH3(CH2)nSH, wheren = 5, 6, 7, 9, 10, 11, 14 and 15 has been followed by carrying out pull-off force measurement using atomic force microscopy (AFM). The self-assembled monolayers on Au(111) surface has been characterized by reflection absorption infra-red spectroscopy (RAIRS) and contact mode AFM. It is observed that the work of adhesion is independent of thiol chain length though the standard deviation is high for short chain length thiol-based monolayers. This may be attributed to the relatively more deformable nature of the short chain thiol films due to their heterogeneity in the monolayer structure than the long chain ones. This, in turn, increases the contact area/volume between the AFM tip and the monolayer, and hence the force of adhesion. However, in the presence of water, the force of adhesion is lower than that observed in air reflecting the effects of capillary forces/polar components associated with the surface energy.
pp 763-768 October 2005
The hydration structure and translocation of an excess proton in hydrogen bonded water clusters of two different sizes are investigated by means of finite temperature quantum simulations. The simulations are performed by employing the method of Car-Parrinello molecular dynamics where the forces on the nuclei are obtained directly from ‘on the fly’ quantum electronic structure calculations. Since no predefined interaction potentials are used in this scheme, it is ideally suited to study proton translocation processes which proceed through breaking and formation of chemical bonds. The coordination number of the hydrated proton and the index of oxygen to which the excess proton is attached are calculated along the simulation trajectories for both the clusters.
Volume 93 | Issue 5
Click here for Editorial Note on CAP Mode