Ferromagnetism at 300 K in spin-coated films of Co doped anatase and rutile-TiO2

Thin films of Ti_1−xCo_xO₂ (x=0 and 0.03) have been prepared on sapphire substrates by spin-on technique starting from metalorganic precursors. When heat treated in air at 550 and 700 °C, respectively, these films present pure anatase and rutile structures as shown both by X-ray diffraction and Raman spectroscopy. Optical absorption indicate a high degree of transparency in the visible region. Such films show a very small magnetic moment at 300 K. However, when the anatase and the rutile films are annealed in a vacuum of 1×10⁻⁵ Torr at 500 and 600 °C, respectively, the magnetic moment, at 300 K, is strongly enhanced reaching 0.36μ_B/Co for the anatase sample and 0.68μ_B/Co for the rutile one. The ferromagnetic Curie temperature of these samples is above 350 K.     

Nitric oxide concentration measurements in atmospheric pressure flames using electronic-resonance-enhanced coherent anti-Stokes Raman scattering

We report the application of electronic-resonance-enhanced coherent anti-Stokes Raman scattering (ERE-CARS) for measurements of nitric oxide concentration ([NO]) in three different atmospheric pressure flames. Visible pump (532 nm) and Stokes (591 nm) beams are used to probe the Q-branch of the Raman transition. A significant resonance enhancement is obtained by tuning an ultraviolet probe beam (236 nm) into resonance with specific rotational transitions in the (v’=0, v”=1) vibrational band of the A²Σ⁺–X²Π electronic system of NO. ERE-CARS spectra are recorded at various heights within a hydrogen-air flame producing relatively low concentrations of NO over a Hencken burner. Good agreement is obtained between NO ERE-CARS measurements and the results of flame computations using UNICORN, a two-dimensional flame code. Excellent agreement between measured and calculated NO spectra is also obtained when using a modified version of the Sandia CARSFT code for heavily sooting acetylene-air flames (φ=0.8 to φ=1.6) on the same Hencken burner. Finally, NO concentration profiles are measured using ERE-CARS in a laminar, counter-flow, non-premixed hydrogen-air flame. Spectral scans are recorded by probing the Q₁ (9.5), Q₁ (13.5) and Q₁ (17.5) Raman transitions. The measured shape of the [NO] profile is in good agreement with that predicted using the OPPDIF code, even without correcting for collisional effects. These comparisons between [NO] measurements and predictions establish the utility of ERE-CARS for detection of NO in flames with large temperature and concentration gradients as well as in sooting environments. PACS 07.88.+y; 42.62.Fi; 42.65.Dr     

MEASUREMENT OF CONTACT ANGLE IN A CLEARANCE-FIT PIN-LOADED HOLE

A simple experimental technique using an instrumented pin was developed for the measurement of the load-contact variation in a clearance-fit, pin-loaded hole. The method is applicable to both conducting and nonconducting materials.     

Engineered protein cages for nanomaterial synthesis

Self-assembled particles of genetically engineered human L subunit ferritin expressing a silver-binding peptide were used as nanocontainers for the synthesis of silver nanoparticles. The inner cavity of the self-assembled protein cage displays a dodecapeptide that is capable of reducing silver ions to metallic silver. This chimeric protein cage when incubated in the presence of silver nitrate exhibits the growth of a silver nanocrystal within its cavity. Our studies indicate that it is possible to design chimeric cages, using specific peptide templates, for the growth of other inorganic nanoparticles.     

Dip-pen nanolithography in tapping mode

Dip-pen nanolithography (DPN) is becoming a popular nano-patterning technique for depositing materials onto a substrate using the probe of an atomic force microscope (AFM). Here, we demonstrate the deposition of a short synthetic peptide by DPN using the Tapping Mode of AFM rather than the commonly used contact mode. DPN in Tapping Mode requires drive amplitude modifications for deposition, yet allows for gentle imaging of the deposited material and enables deposition on soft surfaces.     

Pulse radiolysis of 3-pyridine methanol and 3-pyridine carboxaldehyde in aqueous solutions

Reactions of e_aq ^-, H-atom and OH radicals with 3-pyridine methanol (3-PM) and 3-pyridine carboxaldehyde (3-PCA) have been studied at various pHs using pulse radiolysis technique. e_aq ^- was found to be highly reactive with both 3-PM and 3-PCA (k approx. 10¹⁰ dm³ mol 1 s^-1). Semi-reduced species formed in both cases were strongly reducing in nature. In the case of 3-PM, electron addition leads to the formation of pyridinyl radicals whereas in the case of 3-PCA, PyCHOH type radicals are formed. At pH 6.8, H-atom reaction with 3-PCA also gives semi-reduced species (PyCHOH), whereas at pH 1, H-atoms add to the ring. (CH₃)₂ ^·COH radicals were found to transfer electron to 3-PCA at all the pH values tested and by making use of changes in the absorption spectra, pK _a values of the semi-reduced species were determined to be 4.5 and 10.6. OH radicals were found to undergo addition reaction with 3-PCA, whereas in the case of 3-PM they reacted by H-abstraction as well as addition reaction. By following the yield of methylviologen radical cation formed by electron transfer reaction, it was estimated that approx. 50% of OH radicals react with 3-PM by H-atom abstraction at pH 6.8, giving reducing radicals, whereas at pH 3.2, where 3-PM is in the protonated form, the same is only about 10%. At pH 13, O^-· radical anions were found to react exclusively by H-atom abstraction. Reaction of SO₄ ^-· radicals with 3-PCA was found to give a species identical to the one formed by one electron reduction of nicotinic acid at acidic pH values.     

Heterocyclic nitrogen base adducts of nickel(II)–di(2,4-dibromophenyl)carbazonate

The title complex was prepared and characterized by elemental and spectral analyses. The formation constants of various heterocyclic nitrogen base adducts with the Ni^II–di(2,4-dibromophenyl)carbazonate have been determined in a monophase by spectrophotometry at 25 ± 0.1 °C. The monodenatate and bidentate bases form penta- and hexa-coordinated adducts respectively with 1:1 stoichiometry for the metal chelate-base, whereas the unsaturated monodentate bases form hexa-coordinated adducts with 1:2 stoichiometry. The behaviour of saturated heterocyclic bases such as pyrrolidine, piperidine, hexamethyleneimine and morpholine towards the metal chelate has been studied, and the results are discussed in terms of steric hindrance, basicity and ring structure.     

Microwave assisted low temperature synthesis of sodium zirconium phosphate (NaZr<Subscript>2</Subscript>P<Subscript>3</Subscript>O<Subscript>12</Subscript>)

Sodium zirconium phosphate [NaZr₂P₃O₁₂], a potential ceramic matrix for fixation of high level nuclear waste, was synthesized by heating the mixture of sodium carbonate [Na₂CO₃], zirconyl nitrate hydrate [ZrO(NO₃)₂·5H₂O] and ammonium dihydrogen phosphate [NH₄H₂PO₄] in air, in a resistance heated furnace and a microwave heating system respectively in the temperature range 450 to 650°C. The mixture heated for 1 h in a resistance furnace at 450°C yielded a poorly crystalline NaZr₂P₃O₁₂ [NZP]. Increasing the temperature to 650°C produced a highly crystalline product. The same mixture heated in a microwave oven at 450°C for 1 h however, yielded the most crystalline NZP.In an alternate method, the mixture of sodium dihydrogen phosphate (NaH₂PO₄), zirconium dioxide (ZrO₂) and diammonium hydrogen phosphate [(NH₄)₂HPO₄] heated in resistance furnace at 650°C for the same period did not react in air. It also did not yield the pure product at 450°C when heated in microwave assembly for 1 h.The authors thank the Board of Research in Nuclear Sciences (BRNS) of the Department of Atomic Energy (DAE) for the financial support for this work under the project No. 2000/37/19/BRNS/1959 dtd09-02-02.