Organocatalytic Enantioselective Michael‐Addition of Malonic Acid Half‐Thioesters to β‐Nitroolefins: From Mimicry of Polyketide Synthases to Scalable Synthesis of γ‐Amino Acids

Highly enantioselective biomimetic Michael addition reactions of malonic acid half thioesters (MAHTs) to a variety of nitroolefins, affording the optically active γ‐amino acid precursors, were developed by employing the Cinchona‐based squaramides (up to >99% ee). Remarkably, this biomimetic process is enantioconvergent, a highly desirable feature of a catalytic asymmetric reaction, whereby E/Z‐isomers of the nitroolefins afford the same product enantiomer. The synthetic utility of this organocatalytic protocol was also demonstrated in the formal synthesis of pharmaceutically important γ‐amino acids such as baclofen. Moreover, a quantum chemical analysis of the catalyst‐substrate complexes is shown to give a detailed and instrumental insight into the origin of the observed catalytic activity.     

Two‐pass search strategy using accumulated band energy histogram for HMM‐based identification of perceptually identical music

In this article, we present an efficient two‐pass search strategy for the implementation of a Hidden Markov Model (HMM)‐based music identification system. In our previous work, we demonstrated a single‐pass HMM‐based music identification system, considering its application to music copyright protection. This conventional system showed very robust performance to signal‐level variations between perceptually identical music files. However, it requires heavy computation for search. In the proposed two‐pass search system, the conventional single‐pass search is extended to two‐pass. In pass 1 of the proposed method, a queried music produces an accumulated band energy histogram which is a set of normalized sums of band energies for each frequency bin. This histogram is compared to all of the histograms for the registered music files. The system generates a list of small number of most probable music files among the all of the registered music files. In pass 2, HMM‐based search is applied only to candidate music files selected in pass 1. Using the proposed two‐pass strategy, we successfully implemented a HMM‐based music identification system, which maintains the same level robustness to signal level variations between perceptually identical music files but also produces the identification result very quickly. © 2013 Wiley Periodicals, Inc. Int J Imaging Syst Technol, 23, 127–132, 2013     

Phase transformation and oxidation behavior of Pt-modified MCrAlY coatings

The effects of platinum (Pt) layer on phase transformation and oxidation behavior of MCrAlY (M = Co, Ni) coatings were investigated by isothermal and cyclic oxidation tests at temperature of 1100 °C. Pt layer of about 5 μm thickness was deposited on MAR M247-DS superalloy by an electroplating method, and then the MCrAlY layers were coated with air plasma spray (APS) and vacuum plasma spray (VPS) methods. APS process creates internal oxides and interface voids, whereas the VPS process shows fewer voids in the interface between the MCrAlY layer and the superalloy used as substrate. The oxides and voids formed in the APS process deteriorate the oxidation resistance, indicating that the oxides and voids are transferred to Al₂O₃ compounds during the oxidation tests. The Pt layer shows a strong affinity with Ni element and a weak affinity with Co and Cr elements, resulting in the formation of β-(Ni,Pt)Al phase. The Pt pre-coated layer forces down for the diffusion of soluble elements to get the reduced deplete zone in the superalloy. The VPS process enhances the oxidation resistance of the MCrAlY coating and shows better bonding strength, owing to the generation of homogenous microstructure in the coating and less processing defects.     

Loading algorithms for flexible manufacturing systems with partially grouped unrelated machines and additional tooling constraints

This paper considers the loading problem for flexible manufacturing systems with highly flexible partial machine grouping, i.e., machines are tooled differently, but each operation can be assigned to multiple machines. Loading is the problem of allocating operations and their associated cutting tools to machines for a given set of parts. As an extension of the existing studies, we consider unrelated machines, i.e., processing time of an operation depends on the speed of the machine to which it is allocated, and dedicated machines, i.e., certain part types must be processed on a specific machine. Also, we consider the constraints associated with cutting tools: (a) tool life restrictions and (b) number of available tool copies. An integer linear programming model is suggested for the objective of balancing the workloads assigned to machines and then due to the complexity of the problem, we suggest two-stage heuristics in which an initial solution is obtained using modified bin-packing algorithms and then it is improved by a simple search technique. The two-stage heuristics suggested in this study were tested on various test instances, and the results show that they can give reasonable quality solutions within a very short amount of computation time. Also, a sensitivity analysis was done on the tightness of the tooling constraints, and the results are reported.     

Electrochemical properties of lithium nickel oxide synthesized by the combustion method in an O2 stream

An appropriate mole ratio of urea/nitrate for preheating to synthesize LiNiO₂ was examined by varying the ratio from 1.2 to 9.6. The chemical equation of the combustion reaction was deduced from the XRD analysis result of the mixture after preheating. The XRD pattern of the LiNiO₂ sample calcined at 800 °C for 24 h, after preheating at the mole ratio of urea/nitrate of 3.6 at 400 °C, shows clear split of the 1 0 8 and 1 1 0 peaks, and the largest value of I₀₀₃/I₁₀₄. The sample calcined at 800 °C for 24 h has a relatively high first discharge capacity (164.2 mAh g^?1) and a good cycling performance. Derivative ?dx/|dV| vs. V curve of the LiNiO₂ sample at the voltage range of 2.7–4.4 V for the first cycle exhibits four peaks for charging and discharging, showing that this sample goes through four phase transitions.     

Intracellular drug delivery of layered double hydroxide nanoparticles

Intracellular drug delivery of layered double hydroxide (LDH) nanocarriers have been examined in human osteosarcoma Saos-2 cell culture line by both electron and confocal microscopies. For transmission electron microsopic (TEM) study, LDHs and anticancer drug, methotrexate (MTX) loaded LDHs were synthesized and the particle size was controlled. From the scanning electron microscopic (SEM) studies, morphologies of LDH nanoparticle and its MTX intercalated form were proven to be platelike hexagonal with an average size of approximately 150 nm. In order to understand the cellular penetration behavior, both nanoparticles were treated to human osteosarcoma Saos-2 cell culture lines and the cellular uptake pattern with respect to incubation time was observed by TEM and SEM. We observed that the nanoparticles are attached at the cellular membrane at first and then internalized into the cells via endocytosis within 1 h. Then are located in the intracellular vacuole (endosome). In order to examine the intracellular drug delivery mechanism of LDH nanoparticles, fluorescein 5-isothiocyanate (FITC) labeled MTX was intercalated into LDH and treated on Saos-2 cells. Laser scanning confocal microscopic studies revealed that the FITC-MTX molecules were first internalized with LDH nanocarriers via endocytosis, and located in endosome to deliver loaded drug to target cellular organ. It was, therefore, concluded that LDH could play a role as drug delivery nanocarriers.     

Diffusion control of porous membrane by modifying the nanopore properties

We have investigated the diffusion of various solvents on nanoporous membranes with various pore size and surface energy. We have modified the size of pore channel and surface energy of porous membrane through grafting different sized alkyl chain on inorganic membranes. Typically, disc type zirconia membranes with pore size of 3 nm and silica ones with 1 nm pore were purchased from Inocermic Co. Ltd. (Germany), and the surface and pore channel was modified by either octyltriethoxysilane (OTS) with chain length approximately 1 nm or pentyltriethoxysilane (PTS) with chain length approximately 0.5 nm. The water contact angles of both OTS and PTS grafted membrane were larger than 100 degrees indicating the hydrophobically modified surface. Contact angles of hydrophilic and hydrophobic solvents were also examined to obtain exact surface energy (gamma(sv)) of grafted membrane, and the values were determined to be 56.3, 45.3, and 42.2 mN/m for ungrafted, PTS- and OTS-grafted membrane, respectively. The solvent diffusion patterns were evaluated by measuring the concentration gradient of small dye molecule, azobenzene. The diffusion coefficients of various solvents were measured on the basis of Fick's diffusion law. It was concluded that the diffusivity is dependent on the pore size for solvent with low surface tension and on the gamma(sv) value for solvent with high surface tension.     

Fabrication and characterization of vertically aligned long ZnO nanorods on transparent substrate

Vertically aligned long ZnO nanorods (NRs) were grown by metal organic chemical vapor deposition (MOCVD) technique. Prior to the NRs growth Ga-doped ZnO (GZO) film was deposited by DC sputtering technique on glass substrates. The length and width of the NRs were 25 microm and 450-500 nm, respectively. Structural and optical properties of the NRs were investigated after the growth. The NRs were single crystalline in nature with the preferred growth along c-axis. The diffusion of Ga atoms in the bottom of the NRs during the growth is detected. A prominent near band edge emission of NRs was observed from room-temperature photoluminescence study. Electrical characteristics across the NRs-thin film hybrid structure were measured with UV exposure, where the rise and fall of the photocurrent was exponential in nature due to the desorption and adsorption of oxygen in the surface.