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.     

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.     

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.     

Oxidative cyclization and fragmentation of steroidal alcohols induced by ceric ammonium nitrate

Oxidative cyclizations of steroidal alcohols (1a–1d) using ceric ammonium nitrate (CAN) in aqueous acetonitrile or aqueous acetic acid gave the corresponding cyclic ethers (2a–2d), whereas the tertiary alcohol (4) gave secosteroid (5).     

Efficient terahertz coupling lens based on planar photonic crystals on silicon on insulator

We present a promising coupling device, namely, a terahertz (THz) planar photonic crystal (PhC) lens based on the effective refractive-index contrast between the PhC and the surrounding unpatterned area. Three-dimensional finite-difference time-domain calculations show a 90% power transfer from a 100-microm silicon waveguide to a 10-microm waveguide, and 45% coupling efficiency is confirmed experimentally. These results demonstrate the utility of the PhC lens as an effective approach to coupling into PhC THz circuits.     

Liver metastases from unknown primary site: demonstration on MR images

To demonstrate the MR imaging features of liver metastases in patients with the clinical and histologic diagnosis of tumors of unknown primary tumors, a retrospective 7-year study was performed that included a total of 14 consecutive patients (7 men and 7 women; age range, 39-82 years; mean age, 60.6 years) with liver metastases from unknown primary site who had undergone MR imaging. The following lesion features were evaluated: a) number, b) diameter, c) signal intensity on T1 and T(2)-weighted images, and d) pattern of enhancement on immediate, 45 s and 90 s post gadolinium images. Lesions were classified as hypovascular, hypervascular and nearly isovascular relative to liver parenchyma as shown on immediate post gadolinium images. Patients were separated into four major groups, related to the histologic diagnosis of the lesions: (I) poorly differentiated neoplasms; (II) well-differentiated and moderately differentiated adenocarcinoma; (III) squamous cell carcinoma; (IV) combined poorly differentiated carcinoma and poorly differentiated adenocarcinoma. MRI findings were correlated with histologic information obtained by chart review and confirmed by retrospective histopathology review. All patients had the histologic diagnosis of adenocarcinoma: 8 patients belonged to group II (1 patient with the subtype well-differentiated and 7 patients with the subtype moderately differentiated) and 6 patients to group IV. Eleven patients (79%) presented with multiple lesions distributed throughout both hepatic lobes; 3 patients exhibited solitary lesions. All solitary metastases possessed a diameter equal or larger than 5 cm. Patients with multiple metastases demonstrated a wide range of diameter, ranging from less than 1.5 cm to more than 5 cm. Regarding lesion vascularity, 4 of 13 of the patients had hypovascular metastases and 9 of 13 of the patients had hypervascular lesions. One patient demonstrated both types of lesions. Five of six patients with the histopathologic diagnosis of poorly differentiated adenocarcinoma demonstrated hypervascular metastases. Solitary metastases were most often hypovascular (2 of 3); however no correlation with the histologic subtype was possible. Liver metastases from unknown primary site are often multiple and often hypervascular. Poorly differentiated tumors are the most common histologic type. Metastases are not uncommonly hypovascular, and these are often solitary.     

A specific HPLC-UV method for the determination of cysteine and related aminothiols in biological samples

We present a highly selective and sensitive method for the determination of cysteine (Cys) and related aminothiols that play important roles in health and disease. The key step in the analysis is treatment with 1,1′-thiocarbonyldiimidazole (TCDI) that rapidly and quantitatively reacts with both the amino and thiol groups to form stable cyclic dithiocarbamates with intense UV absorption. Cys, homocysteine (hCys), and cysteinylglycine in plasma (75 μl), urine (100 μl), or cerebrospinal fluid (100–500 μl) were determined by separating and measuring their cyclic derivatives by a high performance liquid chromatograph (HPLC) connected to a UV detector. The chromatograms obtained using TCDI contained fewer and better-resolved peaks than those produced by less selective reagents used previously. Using chemically similar 2-methylcysteine as the internal standard, high repeatability (variation of less than 5%) and adequate sensitivity to detect small increments (10–20%) in the concentrations of cysteinylglycine and hCys were achieved. The HPLC method can also be modified to measure -penicillamine (greater than 0.8 μM) in plasma (50 μl) providing a potential method to monitor plasma levels of this drug in patients.