Structure of a carbon nanotube-dendrimer composite

Using all atomistic molecular dynamics (MD) simulations we report a microscopic picture of the carbon nanotube (6,5)-dendrimer complex for PAMAM dendrimers of generations 2 to 4. We study the compact wrapping conformations of the dendrimer onto the nanotube surface for all the three generations of PAMAM dendrimer. A high degree of wrapping for the non-protonated dendrimer is observed as compared to the protonated dendrimer. For comparison, we also study the interaction of another dendrimer, poly(propyl ether imine) (PETIM), with the nanotube. The results of the distance of closest approach as well as the number of close contacts between the nanotube and the dendrimer reveal that the PAMAM dendrimer interacts strongly as compared to the PETIM dendrimer. We also calculate the binding energy between the nanotube and the dendrimer using MM/PBSA methods and attribute the strong binding to the charge transfer between them. Dendrimer wrapping on the CNT will make it soluble and the dendrimer can act as an efficient dispersing agent for the nanotubes.

A Durable Graphitic-Carbon Support for Pt and Pt3Co Cathode Catalysts in Polymer Electrolyte Fuel Cells

The high efficiency of fuel-cell-powered electric vehicles makes them a potentially viable option for future transportation. Polymer Electrolyte Fuel Cells (PEFCs) are most promising among various fuel cells for electric traction due to their quick start-up and low-temperature operation. In recent years, the performance of PEFCs has reached the acceptable level both for automotive and stationary applications and efforts are now being expended in increasing their durability, which remains a major concern in their commercialization. To make PEFCs meet automotive targets an understanding of the factors affecting the stability of carbon support and platinum catalyst is critical. Alloying platinum (Pt) with first-row transition metals such as cobalt (Co) is reported to facilitate both higher degree of crystallinity and enhanced activity in relation to pristine Pt. But a major challenge for the application of Pt-transition metal alloys in PEFCs is to improve the stability of these binary catalysts. Dissolution of the non-precious metal in the acidic environment could alleviate the activity of the catalysts and hence cell performance. The use of graphitic carbon as cathode-catalyst support enhances the long-term stability of Pt and its alloys in relation to non-graphitic carbon as the former exhibits higher resistance to carbon corrosion in relation to the latter in PEFC cathodes during accelerated-stress test (AST). Changes in electrochemical surface area (ESA), cell performance and charge-transfer resistance are monitored during AST through cyclic voltammetry, cell polarization and impedance measurements, respectively. Studies on catalytic electrodes with X-ray diffraction, Raman spectroscopy and transmission electron microscopy reflect that graphitic carbon-support resists carbon corrosion and helps mitigating aggregation of Pt and Pt3Co catalyst particles. (C) 2012 The Electrochemical Society. DOI: 10.1149/2.051301jes] All rights reserved.

Translocation and encapsulation of siRNA inside carbon nanotubes

We report spontaneous translocation of small interfering RNA (siRNA) inside carbon nanotubes (CNTs) of various diameters and chirality using all atom molecular dynamics simulations with explicit solvent. We use umbrella sampling method to calculate the free energy landscape of the siRNA entry and translocation event. Free energy profiles show that siRNA gains free energy while translocating inside CNT, and barrier for siRNA exit from CNT ranges from 40 to 110 kcal/mol depending on CNT chirality and salt concentration. The translocation time tau decreases with the increase of CNT diameter with a critical diameter of 24 angstrom for the translocation. In contrast, double strand DNA of the same sequence does not translocate inside CNT due to large free energy barrier for the translocation. This study helps in understanding the nucleic acid transport through nanopores at microscopic level and may help designing carbon nanotube based sensor for siRNA. (C) 2013 American Institute of Physics. http://dx.doi.org/10.1063/1.4773302]

A 12 V Substrate-Integrated PbO2-Activated Carbon Asymmetric Hybrid Ultracapacitor with Silica-Gel-Based Inorganic-Polymer Electrolyte

A 12 V Substrate-Integrated PbO2-Activated Carbon hybrid ultracapacitor (SI-PbO2-AC HUCs) with silica-gel sulfuric acid electrolyte is developed and performance tested. The performance of the silica-gel based hybrid ultracapacitor is compared with flooded and AGM-based HUCs. These HUCs comprise substrate-integrated PbO2 (SI-PbO2) as positive electrodes and high surface-area activated carbon with dense graphite-sheet substrate as negative electrodes. 12 V SI-PbO2-AC HUCs with flooded, AGM and gel electrolytes are found to have capacitance values of 308 F, 184 F, and 269 F at C-rate and can be pulse charged and discharged for 100,000 cycles with only a nominal decrease in their capacitance values. The best performance is exhibited by gel-electrolyte HUCs.

Short- and long-term temporal variations in salinity and the oxygen, carbon and hydrogen isotopic compositions of the Hooghly Estuary water, India

The Hooghly River estuary provides a unique experimental site to understand the effect of monsoonal river discharge on freshwater and seawater mixing. Water samples collected bi-weekly for a duration of 17 months were analyzed for salinity, delta O-18,delta C-13(DIC), as well as delta D to investigate the differential mixing of freshwater and seawater. The differences in salinity and delta O-18 of samples collected during low and high tides on the same day are strongly correlated suggesting a well mixed water column at our sampling site. Low salinity and depleted delta O-18 during monsoon is consistent with increased river discharge as well as high rainfall. We identified different slopes in a delta O-18 versus salinity plot for the estuary water samples collected during monsoon and non-monsoon seasons. This is driven by composition of the freshwater source which is dominated by rainwater during monsoon and rivers during non-monsoon months. Selected delta D analyses of samples indicate that groundwater contributes significantly to the Hooghly Estuary during low rainfall times of the year. delta C-13(DIC) measured in the water recorded low values towards the end of monsoon indicating low productivity (i.e. increased organic respiration) while progressively increasing delta C-13(DIC) values from October till January as well as during some of the pre-monsoon months can be explained by increasing productivity. Very low delta C-13(DIC) (similar to-20%0) suggests involvement of carbon derived from anaerobic oxidation of organics and/or methane with potential contribution from increased anthropogenic water supply. An estimate of seawater incursion into the Hooghly Estuary at different times of the year is obtained by using salinity data in a two-component mixing model. Presence of seawater was found maximum (31-37%) during February till July and lowest (less than or equal to 6%) from September till November. We notice a temporal offset between Ganges River discharge farther upstream at Farakka and salinity variation at the Hooghly Estuary. We believe that this time lag is a result of the physical distance between Farakka and Kakdweep (our sampling location) and put constraints on the travel time of river water during early monsoon. (c) 2012 Published by Elsevier B.V.

Measurement and correlation of quaternary solubilities of dihydroxybenzene isomers in supercritical carbon dioxide

The equilibrium quaternary solubilities of dihydroxybenzene (resorcinol + pyrocatechol + hydroquinone + SCCO2) isomers were experimentally determined at 308, 318 and 328K over a pressure range of 9.8-15.7 MPa by using a saturation method. The effects of temperature, pressure and the components on each other have been thoroughly investigated. The selectivity of SCCO2 for ternary (resorcinol + pyrocatechol + SCCO2) and quaternary systems was discussed. A new model equation for quaternary solubilities of solids has been developed by accounting for non-idealities by combining the solution model with Wilson activity coefficient model. The model equation has five adjustable parameters and correlates the quaternary solubilities of current data along with two other quaternary data reported in the literature. (C) 2012 Elsevier B.V. All rights reserved.

Effect of Metal Ions (Ag, Co, Ni, and Pd) on the Visible Light Degradation of Rhodamine B by Carbon-Covered Alumina-Supported TiO2 in Aqueous Solutions

Metal-ion (Ag, Co, Ni, and Pd) doped TiO2 nanocatalysts were successfully embedded on carbon-covered alumina supports. The CCA-embedded catalysts were crystalline and had a high surface area compared to the free metal-ion doped titania nanocatalysts while they still retained the anatase phase of the core TiO2. These catalysts were photocatalytically active under solar light irradiation. Rhodamine B was used as a model pollutant and the reactivity followed a pseudo-first-order reaction kinetics. The reaction rate of the CCA-supported catalysts was Pd > Ag > Co > Ni. Among the ratios of the CCA:catalyst used, it was found that the 1:1 ratio had the fastest reaction rate, followed by the 1:2 ratio, while the 2:1 ratio exhibited the lowest reaction rate. The CCA/metal-ion doped titania were found to have photocatalytic activities comparable with those of CCA-supported titania.

Coupling of photomechanical and electromechanical actuations in carbon nanotubes

It is known that carbon nanotubes (CNTs) possess multifunctional characteristics, which are applicable for a wide variety of engineering applications. CNT is also recognized as a radiation sensitive material, for example for detecting infrared (IR) radiations. One of the direct implications of exposing CNTs to radiation is the photomechanical actuation and generation of a photovoltage/photocurrent. The present work focuses on coupling electromechanical and photomechanical characteristics to enhance the resulting induced-strain response in CNTs. We have demonstrated that after applying an electric field the induced strain in CNT sheet is enhanced to about similar to 2.18 times for the maximum applied electric field at 2 V as compared to the photo-actuation response alone. This enhancement of the strain at higher bias voltages (> 1 V) can be considered as a sum of individual contributions of the bias voltage and IR stimulus. However, at lower voltage (< 1 V) the enhancement in the resulting strain has been attributed to the associated electrostatic effects when CNTs are stimulated with IR radiation under external bias conditions. This report reveals that voltage bias or IR stimulus alone could not produce the observed strain in the CNT sheet under lower bias conditions.

Cu-II-azide polynuclear complexes of Cu-4 building clusters with Schiff-base co-ligands: synthesis, structures, magnetic behavior and DFT studies

Three new copper-azido complexes Cu-4(N-3)(8)(L-1)(2)](n) (1), Cu-4(N-3)(6)(L-2)(2)(H2O)(2)] (2), and Cu-4(N-3)(6)(L-3)(2)](n) (3) L-1 is the imine resulting from the condensation of pyridine-2-carboxaldehyde with N-methylethylenediamine, HL2 and HL3 are the condensation products of 2-hydroxy-3-methoxybenzaldehyde with N,N-diethylethylenediamine and N-ethylethylenediamine respectively] have been synthesized by using 0.5 molar equivalents of the Schiff base ligands with Cu(NO3)(2)center dot 3H(2)O and an excess of NaN3. Single crystal X-ray structures show that the basic unit of these complexes contains very similar Cu-4(II) building blocks. While 1 and 3 have overall 1D structures, 2 forms discrete tetranuclear clusters due to blocking of two coordination sites on the tetranuclear cluster by water molecules. Magnetic susceptibility measurements over a wide range of temperatures exhibit the presence of both antiferromagnetic and ferromagnetic exchanges within the tetranuclear unit structures. Density functional theory calculations (using B3LYP functional and two different basis sets) have been performed on the complexes 1-3 to provide a qualitative theoretical interpretation of their overall magnetic behavior.

Mechanism for the Compressive Strain Induced Oscillations in the Conductance of Carbon Nanotubes

We report on the monotonic increase and the oscillation of electrical conductance in multiwalled carbon nanotubes with compressive strain. Combined experimental and theoretical analyses confirm that the conductance variation with strain is because of the transition from sp(2) to configurations that are promoted by the interaction of walls in the nanotubes. The intrawall interaction is the reason for the monotonic increase in the conduction, while the oscillations are attributable to interwall interactions. This explains the observed electromechanical oscillation in multiwalled nanotubes and its absence in single-walled nanotubes, thereby resolving a long-standing debate on the interpretation of these results. Moreover, the current carrying capability of nanotubes can be enhanced significantly by controlling applied strains. DOI: 10.1103/PhysRevLett.110.095504

Precursors for carbon nitride synthesis

Nano structured carbon nitride films were prepared by pyrolysis assisted chemical vapour deposition. Pyrrole (C4H5N), Pyrrolidine (C4H9N), Azabenzimidazole (C6H5N3) and Triazine (C6H15N3) were used as precursors. The vibrational modes observed for C–N and C  =  N from FTIR spectra confirms the bonding of nitrogen with carbon. XPS core level spectra of C 1s and N 1s also show the formation of bonding between carbon and nitrogen atoms. The nitrogen content in the prepared samples was found to be around 25 atomic %.

Fowler-Nordheim Field Emission from Carbon Nanotubes Under Intense Electric Field

In this paper, we study the Fowler-Nordheim field emission (FNFE) from carbon nanotubes on the basis of a newly formulated electron dispersion law by considering the fact that the intense electric field needed for FNFE changes the band structure in a fundamental way. It has been found that the field emitted current increases with increasing electric field in oscillatory manner due to the appearance of van Hove singularities and exhibits spikes for particular values of the electric field where the singularity occurs. The numerical values of the field emitted current in all the cases vary widely and the determined by the chiral indices and the diameter in the respective cases. The results of this paper find three applications in the fields of nanoscience and technology.

Realistic minimum desorption temperatures and compressor sizing for activated carbon + HFC 134a adsorption coolers

A low thermal diffusivity of adsorption beds induces a large thermal gradient across cylindrical adsorbers used in adsorption cooling cycles. This reduces the concentration difference across which a thermal compressor operates. Slow adsorption kinetics in conjunction with the void volume effect further diminishes throughputs from those adsorption thermal compressors. The problem can be partially alleviated by increasing the desorption temperatures. The theme of this paper is the determination the minimum desorption temperature required for a given set of evaporating/condensing temperatures for an activated carbon + HFC 134a adsorption cooler. The calculation scheme is validated from experimental data. Results from a parametric analysis covering a range of evaporating/condensing/desorption temperatures are presented. It is found that the overall uptake efficiency and Carnot COP characterize these bounds. A design methodology for adsorber sizing is evolved. (c) 2012 Elsevier Ltd. All rights reserved.

Combination of single walled carbon nanotubes/graphene oxide with paclitaxel: a reactive oxygen species mediated synergism for treatment of lung cancer

Heterogeneity in tumors has led to the development of combination therapies that enable enhanced cell death. Previously explored combination therapies mostly involved the use of bioactive molecules. In this work, we explored a non-conventional strategy of using carbon nanostructures (CNs) single walled carbon nanotube (SWNT) and graphene oxide (GO)] for potentiating the efficacy of a bioactive molecule paclitaxel (Tx)] for the treatment of lung cancer. The results demonstrated enhanced cell death following combination treatment of SWNT/GO and Tx indicating a synergistic effect. In addition, synergism was abrogated in the presence of an anti-oxidant, N-acetyl cysteine (NAC), and was therefore shown to be reactive oxygen species (ROS) dependent. It was further demonstrated using bromodeoxyuridine (BrdU) incorporation assay that treatment with CNs was associated with enhanced mitogen associated protein kinase (MAPK) activation that was ROS mediated. Hence, these results for the first time demonstrated the potential of SWNT/GO as co-therapeutic agents with Tx for the treatment of lung cancer.

Clusters of bound particles in the derivative delta-function Bose gas

In this paper we discuss a novel procedure for constructing clusters of bound particles in the case of a quantum integrable derivative delta-function Bose gas in one dimension. It is shown that clusters of bound particles can be constructed for this Bose gas for some special values of the coupling constant, by taking the quasi-momenta associated with the corresponding Bethe state to be equidistant points on a single circle in the complex momentum plane. We also establish a connection between these special values of the coupling constant and some fractions belonging to the Farey sequences in number theory. This connection leads to a classification of the clusters of bound particles associated with the derivative delta-function Bose gas and allows us to study various properties of these clusters like their size and their stability under the variation of the coupling constant. (C) 2013 Elsevier B.V. All rights reserved.