Optical Emission Spectroscopy of Carbon Clusters Produced in a Hollow Cathode Sputter Source

A hollow cathode sputter source is developed to trace the production of carbon clusters and study the influence of discharge current and argon gas pressure on cluster production using an optical emission spectroscopic technique. Optical emission spectra from the hollow cathode source reveal the production of the C₂ Swan band. The sputter source is optimized for the maximum carbon cluster yield. The vibrational temperature analysis of the C₂ cluster is carried out using the Boltzmann plot method. The dependence of vibrational temperature on argon gas pressure is discussed and the dominant method for C-C association in the glow discharge is suggested.     

Micro-structural Impact of Different Strut Shapes and Porosity on Hydraulic Properties of Kelvin-Like Metal Foams

Various ideal periodic isotropic structures of foams (tetrakaidecahedron) with constant ligament cross section are studied. Different strut shapes namely circular, square, diamond, hexagon, star, and their various orientations are modeled using CAD. We performed direct numerical simulations at pore scale, solving Navier–Stokes equation in the fluid space to obtain various flow properties namely permeability and inertia coefficient for all shapes in the porosity range, \(0.60<\varepsilon <0.95\) for wide range of Reynolds numbers, \(10^{-6} . We proposed an analytical model to obtain pressure drop in metallic foams in order to correlate the resulting macroscopic pressure and velocity gradients with the Ergun-like approach. The analytical results are fully compared with the available numerical data, and an excellent agreement is observed.     

Ionic liquid catalyzed synthesis of 7-phenyl-1,4,6,7-tetrahydro-thiazolo[5,4-d]pyrimidine-2,5-diones

A simple, green and catalyst free one pot synthesis of 7-phenyl-1,4,6,7-tetrahydro-thiazolo[5,4-d]pyrimidine-2,5-diones via a multicomponent reaction between thiazolidine-2, 4-dione (TZD), aromatic aldehyde and urea analogues is described. The ionic liquid has been used as a solvent as well as catalyst for this reaction. This reaction proceeded smoothly in good to excellent yields and offered several other advantages including short reaction time, simple experimental workup procedure and no by-products.     

Fortification of CdSe quantum dots with graphene oxide. Excited state interactions and light energy conversion

Graphene based 2-D carbon nanostructures provide new opportunities to fortify semiconductor based light harvesting assemblies. Electron and energy transfer rates from photoexcited CdSe colloidal quantum dots (QDs) to graphene oxide (GO) and reduced graphene oxide (RGO) were isolated by analysis of excited state deactivation lifetimes as a function of degree of oxidation and charging in (R)GO. Apparent rate constants for energy and electron transfer determined for CdSe-GO composites were 5.5 × 10(8) and 6.7 × 10(8) s(-1), respectively. Additionally, incorporation of GO in colloidal CdSe QD films deposited on conducting glass electrodes was found to enhance the charge separation and electron conduction through the QD film, thus allowing three-dimensional sensitization. Photoanodes assembled from CdSe-graphene composites in quantum dot sensitized solar cells display improved photocurrent response (~150%) over those prepared without GO.     

On the role of the three-phase contact line in surface deformation

Viscoelastic braking theories developed by Shanahan and de Gennes and by others predict deformation of a solid surface at the solid-liquid-air contact line. This phenomenon has only been observed for soft smooth surfaces and results in a protrusion of the solid surface at the three-phase contact line, in agreement with the theoretical predictions. Despite the large (enough to break chemical bonds) forces associated with it, this deformation was not confirmed experimentally for hard surfaces, especially for hydrophobic ones. In this study we use superhydrophobic surfaces composed of an array of silicon nanostructures whose Young modulus is 4 orders of magnitude higher than that of surfaces in earlier recorded viscoelastic braking experiments. We distinguish between two cases: when a water drop forms an adhesive contact, albeit small, with the apparent contact angle θ < 180° and when the drop-surface adhesion is such that the conditions for placing a resting drop on the surface cannot be reached (i.e., θ = 180°). In the first case we show that there is a surface deformation at the three-phase contact line which is associated with a reduction in the hydrophobicity of the surface. For the second case, however, there cannot be a three-phase contact line associated with a drop in contact with the surface, and indeed, if we force-place a drop on the surface by holding it with a needle, no deformation is detected, nor is there a reduction in the hydrophobic properties of the surface. Yet, if we create a long horizontal three-phase contact line by partially immersing the superhydrophobic substrate in a water bath, we see a localized reduction in the hydrophobic properties of the surface in the region where the three-phase contact line used to be. The SEM scan of that region shows a narrow horizontal stripe where the nanorods are no longer there, and instead there is only a shallow structure that is lower than the nanorods height and resembles fused or removed nanorods. Away from that region, either on the part of the surface which was exposed to bulk water or the part which was exposed to air, no change in the hydrophobic properties of the surface is observed, and the SEM scan confirms that the nanorods seem intact in both regions.     

Influence of dipole-dipole interactions on coverage-dependent adsorption: CO and NO on Pt(111)

Density functional theory (DFT) calculations of energetic, geometric, vibrational, and electrostatic properties of different arrangements of CO and NO at quarter and half monolayer coverage on Pt(111) are presented. Differences in the extents of electron back-donation from the Pt surface to these molecules cause the low-coverage adsorbate dipoles to have opposite signs at atop and more highly coordinated bridge or fcc sites. These dipoles of opposite sign occupy adjacent positions in the experimentally observed atop-bridge or atop-fcc high -coverage arrangements, leading to attractive electrostatic interactions and concomitant changes in dipole moments, bond lengths, and vibrational frequencies. The interaction energies are estimated by charge partitioning to extract individual dipoles from the mixed arrangement and by calculations of field-dipole interactions. These estimated dipole interactions contribute significantly (20-60%) to the DFT-calculated relative stability of mixed arrangements over atop-, bridge-, or fcc-only arrangements and thus play an important role in coverage-dependent adsorption. We further extend these analyses to a range of molecules with varying dipole moments and show that the general nature of these interactions is not limited to CO and NO.     

Convective rolls and hydrothermal waves in evaporating sessile drops

Recent experiments on the evaporation of sessile droplets have revealed the spontaneous formation of various patterns including the presence of hydrothermal waves. These waves had previously been observed, in the absence of evaporation, in thin liquid layers subjected to an imposed, uniform temperature gradient. This is in contrast to the evaporating droplet case wherein these gradients arise naturally due to evaporation and are spatially and temporally varying. In the present paper, we present a theory of evaporating sessile droplets deposited on a heated surface and propose a candidate mechanism for the observed pattern formation using a linear stability analysis in the quasi-steady-state approximation. A qualitative agreement with experimental trends is observed.     

Release of ultrafine particles from three simulated building processes

Building activities are recognised to produce coarse particulate matter but less is known about the release of airborne ultrafine particles (UFPs; those below 100 nm in diameter). For the first time, this study has investigated the release of particles in the 5–560 nm range from three simulated building activities: the crushing of concrete cubes, the demolition of old concrete slabs, and the recycling of concrete debris. A fast response differential mobility spectrometer (Cambustion DMS50) was used to measure particle number concentrations (PNC) and size distributions (PNDs) at a sampling frequency of 10 Hz in a confined laboratory room providing controlled environment and near–steady background PNCs. The sampling point was intentionally kept close to the test samples so that the release of new UFPs during these simulated processes can be quantified. Tri–modal particle size distributions were recorded for all cases, demonstrating different peak diameters in fresh nuclei (<10 nm), nucleation (10–30 nm) and accumulation (30–300 nm) modes for individual activities. The measured background size distributions showed modal peaks at about 13 and 49 nm with average background PNCs ~1.47 × 10⁴ cm⁻³. These background modal peaks shifted towards the larger sizes during the work periods (i.e. actual experiments) and the total PNCs increased between 2 and 17 times over the background PNCs for different activities. After adjusting for background concentrations, the net release of PNCs during cube crushing, slab demolition, and ‘dry’ and ‘wet’ recycling events were measured as ~0.77, 19.1, 22.7 and 1.76 (×10⁴) cm⁻³, respectively. The PNDs were converted into particle mass concentrations (PMCs). While majority of new PNC release was below 100 nm (i.e. UFPs), the bulk of new PMC emissions were constituted by the particles over 100 nm; ~95, 79, 73 and 90% of total PNCs, and ~71, 92, 93 and 91% of total PMCs, for cube crushing, slab demolition, dry recycling and wet recycling, respectively. The results of this study firmly elucidate the release of UFPs and raise a need for further detailed studies and designing health and safety related exposure guidelines for laboratory workplaces and operational building sites.     

Synthesis,characterization, and in vitro biological studies of some novel pyran fused pyrimidone derivatives

A variety of pyrano[2,3‐d]pyrimidine‐5‐one derivatives 5 , 5a , 5b , 5c , 5d , 5e , 5f , 5g , 5h , 5i , 5j , 6 , 6a , 6b , 6c , 6d , 6e , 6f , 6g , 6h , 6i , 6j have been synthesized from 6‐amino‐4‐(substituted phenyl)‐5‐cyano‐3‐methyl‐1‐phenyl‐1,4‐dihydropyrano[2,3‐c]pyrazole derivatives 4a , 4b , 4c , 4d , 4e , 4f , 4g , 4h , 4i , 4j via cyclization using formic acid and acetic acid. All the newly synthesized compounds have been characterized by IR, ¹H NMR, ¹³C NMR, and elemental analysis. All the synthesized compounds have been screened for antibacterial, antifungal and antitubercular activity. J. Heterocyclic Chem., (2012).     

Solvent and Zn2+ Binding Effects on the Photo-physical Properties of (Dibenzoylmethanato)boron Difluoride

Absorption and emission spectroscopic studies of (dibenzoylmethanato)boron difluoride (1bf) in various polar and non-polar, protic and aprotic solvents are reported. The solvatochromic shifts of the spectral bands were examined in terms of solvent properties, including donor and acceptor numbers, followed by multilinear regression in which several solvent parameters were simultaneously analyzed. This π-conjugated positively charged system exhibits excellent solvatochromism. Variations in the electronic absorption spectral characteristics of 1bf were studied in solution in the presence of zinc perchlorate. Absorption spectral studies indicate stable complex formation between the zinc ion and 1bf in the ground state in aprotic dipolar benzonitrile rather than in protic polar solvent methanol. Zinc ion binding of 1bf was theoretically rationalized through frontier molecular orbital interaction.