A Structural Diversity of Molecular Alkaline-Earth-Metal Polyphosphides: From Supramolecular Wheel to Zintl Ion

A series of molecular group 2 polyphosphides has been synthesized by using air-stable [Cp*Fe(η⁵-P₅)] (Cp*=C₅Me₅) or white phosphorus as polyphosphorus precursors. Different types of group 2 reagents such as organo-magnesium, mono-valent magnesium, and molecular calcium hydride complexes have been investigated to activate these polyphosphorus sources. The organo-magnesium complex [(^DippBDI−Mg(CH₃))₂] (^DippBDI={[2,6-ⁱPr₂C₆H₃NCMe]₂CH}⁻) reacts with [Cp*Fe(η⁵-P₅)] to give an unprecedented Mg/Fe-supramolecular wheel. Kinetically controlled activation of [Cp*Fe(η⁵-P₅)] by different mono-valent magnesium complexes allowed the isolation of Mg-coordinated formally mono- and di-reduced products of [Cp*Fe(η⁵-P₅)]. To obtain the first examples of molecular calcium-polyphosphides, a molecular calcium hydride complex was used to reduce the aromatic cyclo-P₅ ring of [Cp*Fe(η⁵-P₅)]. The Ca-Fe-polyphosphide is also characterized by quantum chemical calculations and compared with the corresponding Mg complex. Moreover, a calcium coordinated Zintl ion (P₇)³⁻ was obtained by molecular calcium hydride mediated P₄ reduction.     

Mechanoluminescence and thermoluminescence of Mn doped ZnS nanocrystals

This paper reports the synthesis of ZnS:Mn nanocrystals by the chemical route in which mercaptoethanol was used as the capping agent. The particle size of such nanocrystals was measured using XRD and TEM patterns and was found to be in between 3and 5 nm. It was found that the peak position of TL glow curve and the TL intensity of ZnS:Mn nanoparticles increases as the particle size is decreased. The isothermal decay technique is used to determine the trap-depth. The stability of the charge carriers in the traps increase with the decrease in size of the nanoparticles. The higher stability may be attributed to the higher surface/volume ratio and also to the increase in the trap-depth with decreasing particle size. When a ZnS:Mn nanocrystal is deformed the peak intensity I_m increases linearly with the increasing height of the load. After I_m, initially the ML intensity decreases at a fast rate, and later on it decreases at a slow rate. The ML in ZnS:Mn nanocrystals can be understood on the basis of the piezoelectrically induced electron detrapping model.     

VEGFR-2 targeted cellular delivery of doxorubicin by gold nanoparticles for potential antiangiogenic therapy

We report a novel gold nanobioconjugate system that achieves targeted delivery of the small molecule drug doxorubicin to endothelial cells using anti-VEGFR-2 antibody conjugated gold nanoparticles (GNPs). The reported nanobioconjugate system combines the inherent ability of GNPs to undergo high levels of derivatization with the precision of antibody recognition of a cell surface antigen. Transmission electron microscopy (TEM) and surface-enhanced Raman spectroscopy (SERS) confirmed intracellular presence of the GNPs. Using a VEGFR-2 expressing cell line and a cell line that is negative for the receptor, in combination with competition assay we established the cell specific targeted delivery of the nanobioconjugate. The nanobioconjugate system described here may have potential drug delivery applications for antiangiogenic cancer therapy.     

Controlled hydrothermal growth of ZnO nanostructures by sequestering the Zn metal ions with the chelating agent EDTA

In the present work, a controlled growth of ZnO nanostructures by manipulating Zn metal ion concentration by the chelating action of ethylene diaminetetra acetic acid in hydrothermal method is studied. EDTA produces metal–chelate complex by the formation of bidentate ligand with Zn²⁺ in the solution and diminishes the reactivity of Zn metal cations. Concentration of EDTA in the mother solution was varied in different ranges like 3, 5 and 10 mM while retaining the zinc metal salt and the NaOH concentration the same. Three different morphologies of wurtzite structured ZnO nanostructures such as nanorods-bunch, separate/discrete uniformly sized hexagonal nanorods and tapered flower petals like shapes are achieved by 3, 5 and 10 mM strengths of EDTA, respectively. The medium concentration 5 mM of EDTA is found to have moderate control over producing ZnO nanostructures of uniform diameter and a high aspect (length to diameter) ratio. An array of vertically aligned free standing ZnO nanorods with uniform spacing is successfully achieved by the addition of 5 mM of EDTA in the mother solution and the same is studied for its fluorescence property at an excitation of 325 nm and it has exhibited a characteristic UV emission of ZnO around 383 nm.     

Simultaneous velocity and temperature measurements in gaseous flow fields using the VENOM technique

We present an initial demonstration of simultaneous velocity and temperature mapping in gaseous flow fields using a new nitric oxide planar laser-induced fluorescence-based method. The vibrationally excited NO monitoring (VENOM) technique is an extension of two-component velocimetry using vibrationally excited NO generated from the photodissociation of seeded NO(2) [Appl. Opt. 48, 4414 (2009)], where the two sequential fluorescence images are obtained probing two different rotational states to provide both velocity and temperature maps. Comparisons to computational fluid dynamics simulations show that the initial VENOM measurements provide good velocity and temperature maps in the relatively high-density regions of the flow, where the rms uncertainties are approximately 5% for velocity and 9% for temperature.     

Engineering the plasmon resonance of large area bimetallic nanoparticle films by laser nanostructuring for chemical sensors

Large area fabrication of metal alloy nanoparticles with tunable surface plasmon resonances on low-cost substrates is reported. A UV excimer laser was used to anneal 5 nm thick Ag Au bilayer films deposited with different composition ratios to create alloy nanoparticles. These engineered surfaces are used to investigate how the wavelength of the surface plasmon resonance affects the optical detection capability of chemical species by surface-enhanced Raman spectroscopy.     

Excimer laser accelerated hydrothermal synthesis of ZnO nanocrystals & their electrical properties

The synthesis of ZnO nanocrystals is reported using a hydrothermal chemical growth technique combined with 248 nm nanosecond excimer laser heating at fluences in the range 0-390 mJ cm⁻². The effect of laser heating in controlling the morphology of the nanocrystals is investigated using optical spectroscopy and electron microscopy characterization. Laser heating is shown to allow control of the crystal morphology from nanoparticles to nanorods as well as to modify the size distributions. The results indicate that not only does the laser accelerate the growth of nanocrystals, but can also produce crystals with a narrow size distribution possibly via photothermal size selection. An initial study of electrical conduction properties of ZnO nanocrystal thin films is also discussed.     

Magnetoelectric behavior of ferrimagnetic BixCo2−xMnO4 (x=0, 0.1 and 0.3) thin films

Thin films of Bi_xCo_2−xMnO₄ (x=0, 0.1 and 0.3) were grown on quartz, LaAlO₃ (LAO) and YBa₂Cu₃O₇ (YBCO) buffer layer coated LAO substrates by pulsed laser deposition (PLD). X-ray diffraction (XRD) and Raman scattering measurements showed that the thin films exhibit single phase polycrystalline cubic spinel structure on all the substrates. Near edge X-ray absorption fine structure (NEXAFS) studies confirmed the octahedral occupancy of the substituted Bi³⁺ ions. Temperature dependent zero-field cooled (ZFC) magnetization measurements show the ferrimagnetic (FM) behavior (T_C∼186 K) and magnetization undergoes a crossover from positive to negative, owing to the opposite contributions of magnetic moments from Co and Mn ions. A weak ferroelectric property exhibited by the films above room temperature was evidenced through the capacitance-voltage (C-V) and dielectric measurements. Magnetoelectric coupling was found to be maximum just below FM-T_C.