Imidazole Functionalized Polyaniline: Synthesis, Characterization, and Cu (II) Coordination Studies

Polyaniline functionalized with imidazole as strategically designed receptor group in its backbone was synthesized for copper binding. The synthesized polymer has been characterized using FTIR, NMR, and UV-Vis spectroscopic techniques. The addition of copper (II) to the polymer distinctly changes the properties such as crystallinity, molecular weight, aggregation, and electronic properties. XRD, DLS, SEM, and four-point probe techniques have been used for study of these changes. It is observed that the secondary ion generated as a result of copper coordination results in the doping of the polyaniline backbone, which enhances the conductivity by one order of magnitude. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 123: 526-534, 2012

Combustion synthesis, characterization and Raman studies of ZnO nanopowders

Spherical shaped ZnO nanopowders (14-50 nm) were synthesized by a low temperature solution combustion method in a short time <5 min. Rietveld analysis show that ZnO has hexagonal wurtzite structure with lattice constants a = 3.2511(1) angstrom, c = 5.2076(2) angstrom, unit cell volume (V) = 47.66(5) (angstrom)(3) and belongs to space group P63mc. SEM micrographs reveal that the particles are spherical in shape and the powders contained several voids and pores. TEM results also confirm spherical shape, with average particle size of 14-50 nm. The values are consistent with the grain sizes measured from Scherrer's method and Williamson-Hall (W-H) plots. A broad UV-vis absorption spectrum was observed at similar to 375 nm which is a characteristic band for the wurtzite hexagonal pure ZnO. The optical energy band gap of 3.24 eV was observed for nanopowder which is slightly lower than that of the bulk ZnO (3.37 eV). The observed Raman peaks at 438 and 588 cm(-1) were attributed to the E(2) (high) and E(1) (LO) modes respectively. The broad band at 564 cm(-1) is due to disorder-activated Raman scattering for the A(1) mode. These bands are associated with the first-order Raman active modes of the ZnO phase. The weak bands observed in the range 750-1000 cm(-1) are due to small defects. (C) 2011 Elsevier B.V. All rights reserved.

Measurement and modeling of Alloy-Spinel-Corundum equilibrium in the Ni-Mn-Al-0 system at 1873 K

The oxygen content of liquid Ni-Mn alloy equilibrated with spinel solid solution, (Ni,Mn)O. (1 +x)A12O3, and α-Al2O3 has been measured by suction sampling and inert gas fusion analysis. The corresponding oxygen potential of the three-phase system has been determined with a solid state cell incorporating (Y2O3)ThO2 as the solid electrolyte and Cr + Cr2O3 as the reference electrode. The equilibrium composition of the spinel phase formed at the interface of the alloy and alumina crucible was obtained using EPMA. The experimental data are compared with a thermodynamic model based on the free energies of formation of end-member spinels, free energy of solution of oxygen in liquid nickel, interaction parameters, and the activities in liquid Ni-Mn alloy and spinel solid solution. Mixing properties of the spinel solid solution are derived from a cation distribution model. The computational results agree with the experimental data on oxygen concentration, potential, and composition of the spinel phase.

Self-Assembly of Metallamacrocycles Using a Dinuclear Organometallic Acceptor: Synthesis, Characterization, and Sensing Study

A dinuclear organometallic acceptor 4,4'-bis[trans-Pt(PEt(3))(2)(O(3)SCF(3))(ethynyl)]biphenyl (1) containing Pt-ethynyl functionality is synthesized. Multinuclear NMR ((1)H, (31)P, and (13)C), infrared (IR), and electrospray ionization mass spectrometry (ESI-MS) including single-crystal X-ray diffraction analysis established the formation of 1. Equimolar treatment of acceptor 1 separately with three different ``clip'' type ditopic donors (L(a)-L(c)) yielded [2 + 2] self-assembled three metallamacrocycles 2a-2c, respectively. These macrocycles were characterized by various spectroscopic techniques, and their sizes/shapes were obtained through geometry optimization using molecular mechanics universal force field (MMUFF) simulations. Attachment of unsaturated ethynyl functionality to biphenyl building unit helped to make the macrocycles (2a-2c) pi-electron rich and thereby fluorescent in nature. Furthermore, 2c in solution has been examined to be suitable for sensing electron-deficient nitroaromatic like picric acid, which is often considered as a secondary chemical explosive. The fluorescence study of 2c showed a marked quenching of initial emission intensity upon titrating with picric acid (PA), and it exhibited the largest fluorescence quenching response with high selectivity among various other electron deficient aromatic compounds tested.

Synthesis, characterization and spectroscopy of composites of graphene with CdSe and CdS nanoparticles

Nanocomposites of few-layer graphene with nanoparticles of CdSe and CdS have been synthesized by two different methods, one involving ultrasonication of a mixture of graphene and the chalcogenide nanoparticles, and another involving assembly at the organic-aqueous interface. The nanocomposites have been examined by electron microscopy, electronic absorption and photoluminescence spectroscopies as well as Raman spectroscopy. Electron microscopy reveals that the nanoparticles are dispersed on the graphene surface. Raman spectra show the presence of definitive electronic interaction between the nanoparticles and graphene depending on the capping agent. Photoluminescence spectra are markedly influenced by the interaction of the nanoparticles with the graphene surface, depending on the capping agent.

Chimeras of Escherichia coli and Mycobacterium tuberculosis Single-Stranded DNA Binding Proteins: Characterization and Function in Escherichia coli

Single stranded DNA binding proteins (SSBs) are vital for the survival of organisms. Studies on SSBs from the prototype, Escherichia coli (EcoSSB) and, an important human pathogen, Mycobacterium tuberculosis (MtuSSB) had shown that despite significant variations in their quaternary structures, the DNA binding and oligomerization properties of the two are similar. Here, we used the X-ray crystal structure data of the two SSBs to design a series of chimeric proteins (m beta 1, m beta 1'beta 2, m beta 1-beta 5, m beta 1-beta 6 and m beta 4-beta 5) by transplanting beta 1, beta 1'beta 2, beta 1-beta 5, beta 1-beta 6 and beta 4-beta 5 regions, respectively of the N-terminal (DNA binding) domain of MtuSSB for the corresponding sequences in EcoSSB. In addition, m beta 1'beta 2(ESWR) SSB was generated by mutating the MtuSSB specific `PRIY' sequence in the beta 2 strand of m beta 1'beta 2 SSB to EcoSSB specific `ESWR' sequence. Biochemical characterization revealed that except for m beta 1 SSB, all chimeras and a control construct lacking the C-terminal domain (Delta C SSB) bound DNA in modes corresponding to limited and unlimited modes of binding. However, the DNA on MtuSSB may follow a different path than the EcoSSB. Structural probing by protease digestion revealed that unlike other SSBs used, m beta 1 SSB was also hypersensitive to chymotrypsin treatment. Further, to check for their biological activities, we developed a sensitive assay, and observed that m beta 1-beta 6, MtuSSB, m beta 1'beta 2 and m beta 1-beta 5 SSBs complemented E. coli Delta ssb in a dose dependent manner. Complementation by the m beta 1-beta 5 SSB was poor. In contrast, m beta 1'beta 2(ESWR) SSB complemented E. coli as well as EcoSSB. The inefficiently functioning SSBs resulted in an elongated cell/filamentation phenotype of E. coli. Taken together, our observations suggest that specific interactions within the DNA binding domain of the homotetrameric SSBs are crucial for their biological function.

Synthesis, structural characterization and ferroelectric properties of Pb(0.76)Ca(0.24)TiO(3) nanotubes

A capillary-enforced template-based method has been applied to fabricate Pb(0.76)Ca(0.24)TiO(3) (PCT24) nanotubes via filling PCT24 precursor solution, prepared by modified sol-gel method, into nanochannels of anodic aluminum oxide templates. The morphology and structure of as-prepared PCT24 were examined by scanning electron microscopy, transmission electron microscopy (TEM) and X-ray diffraction techniques. The obtained PCT24 nanotubes with diameter of similar to 200 nm and wall thickness of similar to 20 nm exhibited a tetragonal perovskite structure. High resolution TEM (HRTEM) analysis confirmed that as-obtained PCT24 nanotubes made up of nanoparticles (5-8 nm) which were randomly aligned in the nanotubes. Formation of some solid crystalline PCT24 nanorods, Y-junctions and multi-branches were observed. Interconnections in the pores of template are responsible for the growth of Y-junctions and multi-branches. The possible formation mechanism of PCT24 nanotubes/nanorods was discussed. Ferroelectric hysteresis loops of PCT24 nanotube arrays were measured, showing a room temperature ferroelectric characteristic of as-prepared PCT24 nanotubes. (C) 2011 Elsevier B.V. All rights reserved.

Gold(I)-selenolate complexes: Synthesis, characterization and ligand exchange reactions

In this paper, the synthesis and characterization of some imidazole-based gold-selenolates are described. This study indicates that the nature of selenolate plays an important role in ligand exchange reactions in gold(I) selenolates. Furthermore, the reactivity of imidazole-based gold(I) selenolates toward nucleophiles such as selenols and phosphines is strikingly different from that of the N,N-dimethylaminobenzylamine-based gold(I) complexes. The presence of Se ... N non-bonded interactions in N,N-dimethylaminobenzylamine-based gold(I) complexes modulates the reactivity of Au(I) centre towards incoming nucleophiles.

Self-assembly of Ru-4 and Ru-8 assemblies by coordination using organometallic Ru(II)(2) precursors: Synthesis, characterization and properties

Coordination-driven self-assembly of binuclear half-sandwich p-cymene ruthenium(II) complexes [Ru-2(mu-eta(4)-C2O4)(MeOH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (1a) or [Ru-2(mu-eta(4)-N,N'-diphenyloxamidato)(MeOH)(2)(eta(6)-p-cymene)(2)]( O3SCF3)(2) (1b) separately with an imidazole-based tetratopic donor L in methanol affords two tetranuclear metallamacrocycles 2a and 2b, respectively. Conversely, the similar combination of L with 2,5-dihydroxy-1,4-benzoquinonato (dhbq) bridged binuclear complex [Ru-2(mu-eta(C6H2O4)-C-4)(MeOH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (1c) in 1:2 molar ratio resulted in an octanuclear macrocyclic cage 2c. All the self-assembled macrocycles 2a-2c were isolated as their triflate salts in high yields and were characterized fully by multinuclear (H-1, C-13 and F-19) NMR, infrared (IR) and electrospray ionization mass spectrometry (ESIMS). In addition, the molecular structure of macrocycle 2a was established unequivocally by single-crystal X-ray diffraction analysis and adopts a tetranuclear rectangular geometry with the dimensions of 5.53 angstrom x 12.39 angstrom. Furthermore, the photo-and electrochemical properties of these newly synthesized assemblies have been studied by using UV-vis absorption and cyclic voltammetry analysis.

Coordination-Driven Self-Assembly of 2D-Metallamacrocycles Using a New Carbazole-Based Dipyridyl Donor: Synthesis, Characterization, and C-60 Binding Study

A new carbazole-based 90 degrees dipyridyl donor 3,6-di(4-pyridylethynyl)carbazole (L) containing carbazole-ethynyl functionality is synthesized in reasonable yield using the Sonagashira coupling reaction. Multinuclear NMR, electrospray ionization-mass spectrometry (ESI-MS), including single crystal X-ray diffraction analysis characterized this 90 degrees building unit. The stoichiometry combination of L with several Pd(II)/Pt(II)-based 90 degrees acceptors (1a-1d) yielded 2 + 2] self-assembled metallacycles (2a-2d) under mild conditions in quantitative yields 1a = cis-(dppf)Pd(OTf)(2); 1b = cis-(dppf)Pt(OTf)(2); 1c = cis-(tmen)Pd(NO3)(2); 1d = 3,6-bis{trans-Pt(C C) (PEt3)(2)(NO3))carbazole]. All these macrocycles were characterized by various spectroscopic techniques, and the molecular structure of 2a was unambiguously determined by single crystal X-ray diffraction analysis. Incorporation of ethynyl functionality to the carbazole backbone causes the resulted macrocycles (2a-2d) to be pi-electron rich and thereby exhibit strong emission characteristics. The macrocycle 2a has a large internal concave aromatic surface. The fluorescence quenching study suggests that 2a forms a similar to 1:1 complex with C-60 with a high association constant of K-sv = 1.0 X 10(5) M-1.

Ultrasonic Guided Wave Characterization and Damage Detection in Foam-core Sandwich Panel using PWAS and LDV

Lamb wave type guided wave propagation in foam core sandwich structures and detectability of damages using spectral analysis method are reported in this paper. An experimental study supported by theoretical evaluation of the guided wave characteristics is presented here that shows the applicability of Lamb wave type guided ultrasonic wave for detection of damage in foam core sandwich structures. Sandwich beam specimens were fabricated with 10 mm thick foam core and 0.3 mm thick aluminum face sheets. Thin piezoelectric patch actuators and sensors are used to excite and sense guided wave. Group velocity dispersion curves and frequency response of sensed signal are obtained experimentally. The nature of damping present in the sandwich panel is monitored by measuring the sensor signal amplitude at various different distances measured from the center of the linear phased array. Delaminations of increasing width are created and detected experimentally by pitch-catch interrogation with guided waves and wavelet transform of the sensed signal. Signal amplitudes are analyzed for various different sizes of damages to differentiate the damage size/severity. A sandwich panel is also fabricated with a planer dimension of 600 mm x 400 mm. Release film delamination is introduced during fabrication. Non-contact Laser Doppler Vibrometer (LDV) is used to scan the panel while exciting with a surface bonded piezoelectric actuator. Presence of damage is confirmed by the reflected wave fringe pattern obtained from the LDV scan. With this approach it is possible to locate and monitor the damages by tracking the wave packets scattered from the damages.

Ag@AgI, Core@Shell Structure in Agarose Matrix as Hybrid: Synthesis, Characterization, and Antimicrobial Activity

A novel in situ core@shell structure consisting of nanoparticles of Ag (Ag Nps) and AgI in agarose matrix (Ag@ AgI/agarose) has been synthesized as a hybrid, in order to have an efficient antibacterial agent for repetitive usage with no toxicity. The synthesized core@shell structure is very well characterized by XRD, UV-visible, photoluminescence, and TEM. A detailed antibacterial studies including repetitive cycles are carried out on Gram-negative Escherichia coli (E. coli) and Gram-positive Staphylococcus aureus (S. aureus) bacteria in saline water, both in dark and on exposure to visible light. The hybrid could be recycled for the antibacterial activity and is nontoxic toward human cervical cancer cells (HeLa cells). The water insoluble Ag@AgI in agarose matrix forms a good coating on quartz, having good mechanical strength. EPR and TEM studies are carried out on the Ag@AgI/agarose and the bacteria, respectively, to elucidate a possible mechanism for killing of the bacteria.

Structural Characterization and Ultraviolet Photoresponse of GaN Nanodots Grown by Molecular Beam Epitaxy

The present work explores the electrical transport and UV photoresponse properties of GaN nanodots (NDs) grown by molecular beam epitaxy (MBE). Single-crystalline wurtzite structure of GaN NDs is verified by X-ray diffraction and transmission electron microscopy (TEM). The interdigitated electrode pattern was created and current-voltage (I-V) characteristics of GaN NDs were studied in a metal-semiconductor-metal configuration. Dark I-V characteristics of lateral grown GaN NDs obeyed the Frenkel-Poole emission model, and the UV response of the device was stable and reproducible with on/off. The responsivity of the detectors is found to be 330 A/W with an external quantum efficiency of 1100%. (C) 2012 The Japan Society of Applied Physics