Synthesis of Nordstrandite and Nordstrandite-Derived Layered Double Hydroxides of Li and Al: A Comparative Study with the Bayerite Counterpart

The layered double hydroxides (LDHs) of Li and Al can be synthesized from the four polymorphs of Al(OH)₃, namely gibbsite, bayerite, nordstrandite, and doyleite. The crystal structure of this class of compounds depends on the type of the precursor used due to their topotactic reaction mechanism. While the LDHs derived from gibbsite and bayerite yield different crystal structures, the incorporation of Li into nordstrandite was expected to yield new LDH structures different from those derived from gibbsite and bayerite. The structure of nordstrandite derived LDHs were however identical to that derived from the bayerite counterpart. The absence of symmetry in the interlayer of nordstrandite (C₁) makes it unsuitable to accommodate the intercalating anions with different molecular symmetries. To make the interlayer gallery suitable for the anions, the metal hydroxide layers of the nordstrandite translate, transforming nordstrandite to bayerite. The bayerite with site symmetries O_h and C₂ stabilizes the anions in the interlayer by hydrogen bonding. The transformation of nordstrandite to bayerite, when soaked in lithium salt solution is, therefore, a manifestation of the intercalating anions.     

Preparation,spectral characterization,and single crystal X-ray structures of cis and trans isomers of 2,4,6-trifluoroethoxy-1,3,5-triethyl-1,3,5,2λ5, 4λ5, 6λ5-triazatriphosphorinane-2,4,6-trioxide, [ETNP(O)(OCH2CF3)]3

Oxidation of the cis isomer of the λ³-cyclotriphosphazane [EtNP(OCH₂CF₃)]₃ with trimethylamine-N-oxide (TMNO) gives the cis isomer of trioxo-λ⁵-cyclotriphosphazane [EtNP(O)(OCH₂CF₃)]₃; the trans isomer of [EtNP(O)(OCH₂CF₃)]₃ is obtained by the treatment of a cis and trans mixture of [EtNP(OCH₂CF₃)]₃ with aqueous H₂O₂. The two trioxocyclotriphosphazanes have been characterized by elemental analysis, IR, and NMR (¹H, ¹³C, ¹⁹F, and ³¹P) spectroscopy. The solid state structures of both the isomers have been determined by single crystal X-ray diffraction. The six-membered P₃N₃ ring in both the isomers exhibits a twist-boat conformation; in the cis isomer, the trifluoroethoxy substituents lie on the same side of the ring, whereas, in the trans isomer, two trifluoroethoxy groups are on one side of the ring and the third on the other side of the ring. Crystal data for cis-[EtNP(O)(OCH₂CF₃)]₃: monoclinic, P 2₁/ n , a = 13.593(3), b = 9.721(2), c = 17.539(3) Å, β = 99.49(2)°, V = 2286(1) ų, Z = 4, and Final R = 0.047. Crystal data for trans-[EtNP(O)(OCH₂CF₃)]₃: monoclinic, P 2₁/ n , a = 11.685(4), b = 15.115(5), c = 13.233(5) Å, - = 102.21(3)°, V = 2284(1) ų, Z = 4, and Final R = 0.078.     

Alkylation of catechol with methanol to guaiacol over sulphate-modified zirconia solid acid catalysts

A series of sulphate-promoted ZrO₂ solid acid catalysts with different contents of SO₄ ²⁻ were calcined at 450°C in air for 4 h and tested for the liquid-phase alkylation of catechol to guaiacol in a fixed-bed down-flow reactor. The 5 wt.% SO₄ ²⁻ on ZrO₂ showed the best conversion (82%) and selectivity for guaiacol (84%) at 200°C and 1 bar pressure. A smooth correlation was observed between the catalytical activity and surface acidity of sulphated zirconia. Based on our results, a surface mechanism is proposed.     

Grain Boundary Sliding and Slip Transmission in High Purity Aluminum

Despite its significance in polycrystalline materials, there have been few experimental investigations of the activity of grain boundary sliding (GBS) and the relationship between GBS and slip transmission at grain boundaries. The present work addresses this knowledge gap by the characterization of full-field strain and microstructural information in an experimental system of high-purity (99.99%) columnar aluminum subjected to uniaxial tension at 190 °C. High-resolution, full-gage strain fields were characterized on an unloaded specimen by distortion-corrected and stitched scanning electron microscope-enabled digital image correlation (SEM-DIC). Alignment between the lower-resolution electron backscatter diffraction (EBSD) and higher-resolution strain fields was significantly improved by clustering of strain data within an EBSD-defined boundary mantle. Grain boundary sliding was investigated at select boundaries, and it was determined that GBS magnitude profiles can have large gradients along a single boundary and vary significantly between boundaries. Using a geometric compatibility factor (m′) to quantify favorability of slip transmission, the two grain boundaries that exhibited the largest average GBS magnitude experienced contiguous slip on moderately well aligned slip systems, although the exact nature of this slip activity, whether transmission or nucleation, remains under investigation.

     

Analysis of current voltage characteristics of MWIR homojunction photodiodes for uncooled operation

Dark currents n⁺/ν/p⁺ Hg_0.69Cd_0.31Te mid wave infrared photodiodes were measured at room temperature. The diodes exhibited negative differential resistance at room-temperature, but with increasing leakage currents as a function of reverse bias. The current–voltage characteristics were simulated and fitted by incorporating trap assisted tunneling via traps and Shockley–Read–Hall generation recombination process due to dislocations in the carrier transport equations. The thermal suppression of carriers was simulated by taking energy level of trap (E_t), trap density (N_t) and the doping concentrations of n⁺ and ν regions as fitting parameters. Values of E_t and N_t were 0.78E_g and ～6–9 × 10¹⁴ cm^?3 respectively for most of the diodes. Variable temperature current voltage measurements on variable area diode array (VADA) structures confirmed the fact that variation in zero bias resistance area product (R₀A) is related to g–r processes originating from variation in concentration and kind of defects that intersect a junction area.     

An improved Hardy-Sobolev inequality and its application

For , a bounded domain, and for , we improve the Hardy-Sobolev inequality by adding a term with a singular weight of the type . We show that this weight function is optimal in the sense that the inequality fails for any other weight function more singular than this one. Moreover, we show that a series of finite terms can be added to improve the Hardy-Sobolev inequality, which answers a question of Brezis-Vazquez. Finally, we use this result to analyze the behaviour of the first eigenvalue of the operator as increases to for .

     

Spontaneous assembly of a hydrogen-bonded tetrahedron

Triphenylamine ortho-tricarboxylic acid (1) has been synthesized and the crystal structure reported. This molecule is shown to spontaneously self-assemble into a hydrogen-bonded tetrahedron. Furthermore, Electrospray Ionization Mass Spectroscopy shows evidence for the stability of such aggregates from an ethanol/water solution.     

A novel approach to combinatorial library design

We address the problem of designing a general-purpose combinatorial library to screen for pharmaceutical leads. Conventional approaches focus on diversity as the primary factor in designing such libraries. We suggest making screening libraries out of a set of pharmaceutically relevant scaffolds, with multiple analogs per scaffold. The rationale for this rests on the fact that even though the hit-rate in active series is much higher than in the database as a whole, often a large fraction of the compounds in active series are inactive. This is especially true when the series has not been optimized for the target under study. We introduce the concept of hit-rate within a series and use historic screening data to arrive at a crude estimate for it. We then use simple probability arguments to show that 50-100 compounds are required in each series in order to be nearly certain of finding at least one active compound in each true active series for any given target.     

High-efficiency coupling structure for a single-line-defect photonic-crystal waveguide

We present the design and fabrication of a planar structure for coupling light from a multimode feed waveguide into a single-line-defect photonic-crystal waveguide. Finite-difference time-domain calculations predict a coupling efficiency of greater than 90%, and preliminary experimental results indicate successful coupling through a single-line-defect photonic-crystal waveguide. Device design, fabrication, and characterization are presented.