A theoretical approach for accurate predictions of the enthalpies of formation of carotenes

A computational approach has been designed for accurately determining enthalpies of formation (ΔH(f)) for the carotene species. This approach, named correlation corrected atomization (CCAZ), is based on the concept of bond and group additivity, and is applied along with density functional theory (DFT). Corrections to the deficiencies in DFT were divided into 1,2-, 1,3-, and 1,4- atomic interactions, which were determined by comparisons with the G3 data of the training set. When comparing predictions from CCAZ combined with two different DFT methods (B3LYP and MPWB1K), fairly accurate prediction is expected. In contrast, DFT using the atomization and isodesmic schemes resulted in poor predictions of ΔH(f). The equivalent methods, atomic equivalent (AEQ) and group equivalent (GEQ) provide improved predictions; however, the accuracies are lower than that of CCAZ.     

Determination of the series resistance under the Schottky contacts of AlGaN/AlN/GaN Schottky barrier diodes

Rectangular AlGaN/AlN/GaN heterostructure field-effect transistors (HFETs) were fabricated,and the gate and the source of the HFETs consisted of AlGaN/AlN/GaN Schottky barrier diodes (SBDs).Based on the measured forward current-voltage and the capacitance-voltage characteristics of the AlGaN/AlN/GaN SBDs,the series resistance under the Schottky contacts (RS) was calculated using the method of power consumption,which has been proved to be valid.Finally,the method of power consumption for calculating R S was successfully used to study the two-dimensional electron gas electron mobility for a series of circular AlGaN/AlN/GaN SBDs.It is shown that the series resistance under the Schottky contacts cannot be neglected and is important for analysing and characterizing the AlGaN/AlN/GaN SBDs and the AlGaN/AlN/GaN HFETs.     

Ionothermal synthesis of metal oxalatophosphonates with a three-dimensional framework structure: Na2M3(C2O4)3(CH3PO3H)2 (M = FeII and MnII)

Two isostructural transition-metal oxalatophosphonates, Na2M3(C2O4)3(CH3PO3H)2 (M = Fe(II) and Mn(II)), have been synthesized by using a low-melting-point eutectic mixture of choline chloride and malonic acid as a solvent and characterized by single-crystal X-ray diffraction and 57Fe M?ssbauer spectroscopy. The 3D framework structure consists of a corner-sharing octahedral trimer that is linked with other trimers through two distinct oxalate ligands with unusual linkage types, phosphonate tetrahedra, and H bonds to form infinite channels along the [101] direction where the Na+ cations are located. They are the first examples for the use of an ionic liquid as a solvent in the synthesis of metal oxalatophosphonates. Crystal data for the Fe compound follow: monoclinic, P2(1)/n (No. 14), a = 5.8063(1) A, b = 10.3867(3) A, c = 14.8094(4) A, beta = 96.926(1) degrees , and Z = 2. Crystal data for the Mn compound are the same as those for the Fe compound except a = 5.8734(9) A, b = 10.557(2) A, c = 14.863(2) A, and beta = 96.691(2) degrees .     

Multilayer resonances sharpened by grating waveguide resonance

A multilayer planar structure comprising a highly reflective multilayer dielectric mirror and a corrugated waveguide is proposed for use as a narrow passband optical filter. The proposed filter has a much narrower linewidth than a usual Fabry–Perot cavity with two multilayer dielectric mirrors. It is shown that the narrowing of the linewidth is due to the strong spectral dependence of the phase of the wave reflected from the waveguide grating mirror. The shape of the pass band can be made symmetrical by a proper choice of the grating groove profile.     

Accurate prediction of the enthalpies of formation for xanthophylls

This study investigates the applications of computational approaches in the prediction of enthalpies of formation (ΔH(f)) for C-, H-, and O-containing compounds. Molecular mechanics (MM4) molecular mechanics method, density functional theory (DFT) combined with the atomic equivalent (AE) and group equivalent (GE) schemes, and DFT-based correlation corrected atomization (CCAZ) were used. We emphasized on the application to xanthophylls, C-, H-, and O-containing carotenoids which consist of ～ 100 atoms and extended π-delocaization systems. Within the training set, MM4 predictions are more accurate than those obtained using AE and GE; however a systematic underestimation was observed in the extended systems. ΔH(f) for the training set molecules predicted by CCAZ combined with DFT are in very good agreement with the G3 results. The average absolute deviations (AADs) of CCAZ combined with B3LYP and MPWB1K are 0.38 and 0.53 kcal/mol compared with the G3 data, and are 0.74 and 0.69 kcal/mol compared with the available experimental data, respectively. Consistency of the CCAZ approach for the selected xanthophylls is revealed by the AAD of 2.68 kcal/mol between B3LYP-CCAZ and MPWB1K-CCAZ.     

Cs2USi6O15: a tetravalent uranium silicate

A uranium(IV) silicate has been synthesized under high-temperature, high-pressure hydrothermal conditions. The structure consists of unbranched dreier single layers with the composition [Si(2)O(5)] that are connected by UO(6) octahedra to form a 3D framework with 7-ring channels where the Cs(+) cations are located. Each UO(6) octahedron spans four neighboring dreier single chains and, therefore, introduces a high degree of corrugation in the silicate layers. The U 4f X-ray photoelectron spectroscopy spectrum was measured to confirm the valence state of the uranium. A comparison of related metal silicate structures is made. After the synthesis of this compound, all members in the family of uranium silicates and germanates with oxidation states of uranium from 4+ to 6+ have been observed.     

Cs4UGe8O20: a tetravalent uranium germanate containing four- and five-coordinate germanium

A very rare tetravalent uranium germanate has been synthesized under hydrothermal conditions at 585 °C and 160 MPa. Its structure contains layers of single-ring Ge(3)O(9)(6-) germanate anions that are connected by UO(6) octahedra and dimers of edge-sharing GeO(5) trigonal bipyramids to form a three-dimensional framework with intersecting 6- and 7-ring channels. UV-visible, photoluminescence, and U 4f X-ray photoelectron spectroscopy were used to confirm the valence state of uranium.     

Aspochalasin H1: A New Cyclic Aspochalasin from Hawaiian Plant-Associated Endophytic Fungus Aspergillus sp. FT1307

Aspergillus is one of the most diverse genera, and it is chemically profound and known to produce many biologically active secondary metabolites. In the present study, a new aspochalasin H1 (1), together with nine known compounds (2–10), were isolated from a Hawaiian plant-associated endophytic fungus Aspergillus sp. FT1307. The structures were elucidated using nuclear magnetic resonance (NMR) (¹H, ¹H-¹H COSY, HSQC, HMBC, ROESY and 1D NOE), high-resolution electrospray ionization mass spectroscopy (HRESIMS), and comparisons with the reported literature. The absolute configuration of the new compound was established by electronic circular dichroism (ECD) in combination with NMR calculations. The new compound contains an epoxide moiety and an adjacent trans-diol, which has not been reported before in the aspochalasin family. The antibacterial screening of the isolated compounds was carried out against pathogenic bacteria (Staphylococcus aureus, Methicillin-resistant S. aureus and Bacillus subtilis). The antiproliferative activity of compounds 1–10 was evaluated against human breast cancer cell lines (MCF-7 and T46D) and ovarian cancer cell lines (A2780).