Anomalous temperature dependence of phonons and photoluminescence bands in pyrochlore Er2Ti2O7: signatures of structural deformation at 130 K

We report a Raman study of single crystal pyrochlore Er(2)Ti(2)O(7) as a function of temperature from 12 to 300 K. In addition to the phonons, various photoluminescence (PL) lines of Er(3+) in the visible range are also observed. Our Raman data show an anomalous red-shift of two phonons (one at ~200 cm(-1) and another at ~520 cm(-1)) upon cooling from room temperature which is attributed to phonon-phonon anharmonic interactions. However, the phonons at ~310, 330, and 690 cm(-1) initially show a blue-shift upon cooling from room temperature down to about 130 K, followed by a red-shift, indicating a structural deformation at ~130 K. The intensities of the PL bands associated with the transitions between the various levels of the ground state manifold ((4)I(15/2)) and the (2)H(11/2) as well as (4)S(3/2) excited state manifolds of Er(3+) show a change at ~130 K. Moreover, the temperature dependence of the peak position of the two PL bands shows a change in their slope (dω/dT) at ~130 K, thus further strengthening the proposal of a structural deformation. The temperature dependence of the peak positions of the PL bands has been analyzed using the theory of optical dephasing in crystals.     

Effect of electric field on the rheological and dielectric properties of a liquid crystal exhibiting nematic-to-smectic-A phase transition

We report simultaneous measurements of shear viscosity (η) and dielectric constant (ε) of octyloxy cyanobiphenyl (8OCB) in the nematic (N) and smectic-A (SmA) phases as functions of temperature and electric field. With increasing electric field η increases in the N phase whereas it decreases in the SmA phase and saturates beyond a particular field in both the phases. The flow curves in the intermediate-field range show two Newtonian regimes in the N phase. The temperature-dependent behavior of η and ε at zero or at small electric field suggests the occurrence of several structures that results from precessional motion of the director along the neutral direction as reported in similar other system. We show that the precessional motions are gradually suppressed with increasing electric field and the effective viscosity resembles with the Miesowicz viscosity η ₁ at high enough electric field. In the intermediate field range the temperature-dependent η exhibits anomalous behavior across the N-SmA phase transition which is attributed to the large contribution of Leslie coefficient α ₁.     

Multicomponent assembly of anionic and neutral decanuclear copper(II) phosphonate cages

A multicomponent synthetic strategy involving copper(II) ions, tert-butylphosphonic acid (t-BuPO(3)H(2)) and 3-substituted pyrazole ligands has been adopted for the synthesis of soluble molecular copper(II) phosphonates. The use of six different 3-substituted pyrazoles, 3-R-PzH [R = H, Me, CF(3), Ph, 2-pyridyl (2-Py), and 2-methoxyphenyl (2-MeO-C(6)H(4))] as ancillary ligands afforded nine different decanuclear cages, [Cu(5)(μ(3)-OH)(2)(O(3)P-t-Bu)(3)(3-R-Pz)(2)(X)(2)](2)·(Y) where R = H, X = t-BuPO(3)H, and Y = (Et(3)NH(+))(4)(solvent) (1); R = Me, X = 3-MePzH, and Y = solvent (2); R = Me, X = t-BuPO(3)H, and Y = (Et(3)NH(+))(4)(solvent) (3); R = CF(3), X = t-BuPO(3)H, and Y = (Et(3)NH(+))(4)(solvent) (4); R = Ph, X = 3-PhPzH, and Y = solvent (5); R = 2-Py, X = 0.5 MeOH, and Y = solvent (6); R = 2-Py, X = none, and Y = solvent (7); R = 2-Py, X = H(2)O, and Y = (Et(3)NH(+)·PF(6)(-))(2)(solvent) (8); R = 2-MeO-C(6)H(4), X = MeOH or 0.5:0.5 MeOH/H(2)O, and Y = solvent (9). Compounds 1-6, 8, and 9 were isolated using a direct synthetic method which involves the reaction of copper(II) salts and the ligands, while 7 was obtained from an indirect route involving the reaction of preformed copper-pyridylpyrazolate precursor complexes and t-BuPO(3)H(2). The decametallic compounds 1-9 possess a butterfly shaped core. The core of the cages 1, 3, and 4 are tetraanionic and contain more phosphonates than pyrazole ligands, while the other cages are neutral and contain more pyrazoles than phosphonate ligands. Compounds 1-6 have been studied by electrospray ionization-high-resolution mass spectrometry (ESI-HRMS). The decanuclear cage 6 was shown to be a good plasmid modifier.     

Can commonly used hydrazine produce n-type graphene?

A simple chemical method to obtain bulk quantities of N-doped, reduced graphene oxide (rGO) sheets (see figure) as an n-type semiconductor through the treatment of as-prepared GO sheets with the commonly used reducing reagent hydrazine, followed by rapid thermal annealing (RTA) is described.     

Power Values of Derivations with Annihilator Conditions on Lie Ideals in Prime Rings

Let R be a prime ring of char R ≠ 2, d a nonzero derivation of R, U a noncentral Lie ideal of R, and a ∈ R. If au ^{n ₁} d(u) ^{n ₂} u ^{n ₃} d(u) ^{n ₄} u ^{n ₅} … d(u) ^{n _k?1} u ^{n _k}  = 0 for all u ∈ U, where n ₁, n ₂,…,n _k are fixed non-negative integers not all zero, then a = 0 and if a(u ^s d(u)u ^t ) ⁿ  ∈ Z(R) for all u ∈ U, where s ≥ 0, t ≥ 0, n ≥ 1 are some fixed integers, then either a = 0 or R satisfies S ₄, the standard identity in four variables.     

Optical and Structural Properties of Ammonia-Free Amorphous Silicon Nitride Thin Films for Photovoltaic Applications

Hydrogenated amorphous silicon nitride (a-SiN_x:H) thin films have been deposited through the green chemistry route using silane (SiH₄) and nitrogen (N₂) as process gases with SiH₄ flow being variable and N₂ flow being constant without the use of pollutant and corrosive ammonia (NH₃) by the plasma-enhanced chemical vapor deposition technique at 13.56 MHz. Fourier transform infrared spectroscopy analysis shows various possible vibrational modes of Si-H, Si-N, and N-H bonds present in the film. Raman spectroscopy is performed on these samples to calculate volume fractions corresponding to amorphous phases present in the a-SiN_x:H films. The refractive index (η) values are calculated using Swanepoel's method, which are in the range of 2.89 to 3.17. The thickness of the deposited films has been evaluated using transmission spectra. Absorption coefficient and band gap (E _g) values are obtained from optical absorption studies. An increase in the E _g and a decrease in the η value have been observed for the samples grown with decreasing SiH₄ flow.     

Synchrotron‐induced EDXRF determination of uranium and thorium in mixed uranium–thorium oxide pellets

Uranium and thorium in their mixed oxides were determined by synchrotron‐induced energy dispersive X‐ray fluorescence (EDXRF) spectrometry. Mixed oxide calibration mixtures containing uranium and thorium in different relative amounts and approximately fixed amount of yttrium were prepared in the form of pellets. The EDXRF spectra of the pellets were measured at the microfocus XRF (BL‐16) beam line of Indus‐2 synchrotron radiation facility (Raja Ramanna Centre of Advanced Technology, Indore, India). Characteristic X‐ray lines U Lα, Th Lα, and Y Kα were used as analyte lines. Calibration plot for the determination of uranium was prepared by plotting amount ratios of U and Y against the intensity ratios of U Lα and Y Kα. Similarly, a calibration plot for thorium analysis was also made. The amounts of uranium and thorium in the sample mixtures prepared in similar way as the calibration mixtures were determined using the aforementioned calibration plots. The precision values obtained for uranium and thorium determinations were found to be 0.3 and 0.2% (relative standard deviation, 1σ), respectively. The EDXRF results deviated from the expected values by 1% for uranium and 0.9% for thorium determinations. These analytical features are much superior compared with laboratory‐based analysis results. Copyright © 2012 John Wiley & Sons, Ltd.     

The Imidazopyridine Derivative JK184 Reveals Dual Roles for Microtubules in Hedgehog Signaling

Eradicating hedgehogs : The title molecule has been previously identified as a potent inhibitor of the Hedgehog signaling pathway, which gives embryonic cells information needed to develop properly. This molecule is shown to modulate Hedgehog target gene expression by depolymerizing microtubules, thus revealing dual roles of the cytoskeleton in pathway regulation (see figure).

     

Vanishing power values of commutators with derivations

Let R be a prime ring of char R ≠ 2, let d be a nonzero derivation of R, and let ρ be a nonzero right ideal of R such that [[d(x)x ⁿ , d(y)] _m , [y, x] _s ] ^t = 0 for all x, y ? ρ, where n ≥ 1, m ≥ 0, s ≥ 0, and t ≥ 1 are fixed integers. If [ρ, ρ]ρ ≠ 0 then d(ρ)ρ = 0.     

Propargyloxycarbonyl (Poc) amino acid chlorides as efficient coupling reagents for the synthesis of 100% diastereopure peptides and resin bound tetrathiomolybdate as an effective deblocking agent for the Poc group

Synthesis of short peptides using propargyloxycarbonyl amino acid chlorides as effective coupling reagents and polymer supported tetrathiomolybdate as an efficient deblocking agent are reported.