Active control of lifted diffusion flames with arrayed micro actuators

Active control of a lifted flame issued from a coaxial nozzle is investigated. Arrayed micro flap actuators are employed to introduce disturbances locally into the initial shear layer. Shedding of large-scale vortex rings is modified with the flap motion, and the flame characteristics such as liftoff height, blowoff limit, and emission trend, are successfully manipulated. Spatio-temporal evolution of large-scale vortical structures and fuel concentration is examined with the aid of PIV and PLIF in order to elucidate the control mechanisms. It is found that, depending on the driving signal of the flaps, the near-field vortical structures are significantly modified and two types of lifted flames having different stabilization mechanisms are realized.     

A Direct,Concise, and Enantioselective Synthesis of 2‐Substituted 4,4,4‐Trifluorobutane‐1,3‐diols Based on the Organocatalytic In Situ Generation of Unstable Trifluoroacetaldehyde

A direct, concise, and enantioselective synthesis of 2‐substituted 4,4,4‐trifluorobutane‐1,3‐diols based on the organocatalytic asymmetric direct aldol reaction of an ethyl hemiacetal of trifluoroacetaldehyde with various aldehydes was examined. A catalytic amount (30 mol %) of commercially available and inexpensive l ‐prolinamide is quite effective as an organocatalyst for the catalytic in situ generation of gaseous and unstable trifluoroacetaldehyde from its hemiacetal, and a successive asymmetric direct aldol reaction with various aldehydes in dichloromethane at 0 °C, followed by reduction with sodium borohydride, gives 2‐substituted 4,4,4‐trifluorobutane‐1,3‐diols in moderate to good yields (31–84 %) with low diastereoselectivities and good to excellent enantioselectivities (64–97 % ee).     

Multispectral filter array design without training images

Multispectral images (MSIs) have been studied for many applications; however, limitations persist in techniques to capture them due to the complexity of assembling one or more prisms and multiple sensor arrays in order to detect signals. Inspired by the application of color filter arrays to commercial digital RGB cameras, a number of researchers have studied multispectral filter arrays (MSFAs) to solve this problem. Determining the measurement wavelength and pattern of an MSFA is important for improving the quality of the demosaicked image. Some conventional studies for designing MSFAs have used training data and have optimized the measurement wavelengths and the pattern by iteratively minimizing the error between the training data and the demosaicked images. We propose a metric to evaluate an MSFA without MSIs, and optimize the measurement wavelengths and the pattern of the MSFA by minimizing the metric. The proposed metric measures the sampling distance between filters in a spatial–spectral domain and quantifies the dispersion of the sampling points by average nearest-neighbor distance (ANND) under a given arbitrary MSFA. Since the quality of the demosaicked image is assumed to be proportional to the degree of dispersion of the sampling points in the spatial–spectral domain, we optimize the MSFA by minimizing the ANND in a nested simulated annealing process. Experimental results show that the optimized MSFA obtained using our method attained a higher peak signal-to-noise ratio (PSNR) than conventional untrained MSFAs in many cases. In addition, the performance difference between some trained MSFAs and the proposed MSFA was small. We also confirmed the validity of the proposed ANND by a comparison with the mean square error obtained from MSI datasets.     

Computational studies on nonenzymatic pyroglutamylation mechanism of N-terminal glutamic acid residues in aqueous conditions*

Spontaneous cyclisation of glutamic acid (Glu) residues located at N-termini in peptides and proteins is called ‘pyroglutamylation’ and is assumed to be involved in several neurodegenerative diseases. Although it has long been believed that N-terminal Glu residues undergo pyroglutamylation enzymatically, it has recently been experimentally confirmed that nonenzymatic pyroglutamylation can proceed in some types of aqueous buffer. However, the detailed mechanism has not been proposed or investigated, and even whether some small-molecule catalysts are required for pyroglutamylation has not been clarified. Therefore, we investigated three types of pyroglutamylation mechanism of N-terminal Glu residues using quantum chemical calculations: in the absence of any catalysts, catalysed by one water molecule, and catalysed by two water molecules. All calculations were performed using N-terminal Glu residues capped with a methylamino group on the C-terminal as a model compound. Optimised energy minima and transition state geometries were obtained using the B3LYP density functional method. The pyroglutamylation mechanism is roughly divided into two steps: cyclisation and dehydration, and the calculated activation barrier was 108 and 107?kJ mol^?1 in the two- and three-water-assisted pathways, respectively. The results of computational analysis suggest that water molecules can act as catalysts for pyroglutamylation.

The calculated activation barrier of two-water-assisted pyroglutamylation was 108?kJ mol^?1, and the results of computational analysis indicate that water molecules can act as catalysts for pyroglutamylation.     

Cross-shaped photoluminescence of excimers in perylene crystals

Cross-shaped excimer (self-trapped exciton) luminescence from α- and β-perylene single crystals of 50–100 μm was found when they were excited at the center of the crystals with a continuous-wave (cw) laser resonant with the exciton absorption. The cross shape is formed by the two lines which intersect at the excited position and are perpendicular to the sides of the crystals of parallelogram shape. Luminescence is emitted from the excited spot and 4 side edges in the cross shape. The most striking feature is that the luminescence intensity at the edges was as high as or higher than at the excited spot. The possibility of the exciton propagation or the waveguide effect is rejected both experimentally and theoretically. This phenomenon can be reasonably explained only when the radiative transition probability of excimers is significantly enhanced at the crystals side edges than at the center due to the lower symmetry.     

Photocatalytic CO2 Reduction under Visible-Light Irradiation by Ruthenium CNC Pincer Complexes

Photocatalytic CO₂ reduction using a ruthenium photosensitizer, a sacrificial reagent 1,3-dimethyl-2-(o-hydroxyphenyl)-2,3-dihydro-1H-benzo[d]imidazole (BI(OH)H), and a ruthenium catalyst were carried out. The catalysts contain a pincer ligand, 2,6-bis(alkylimidazol-2-ylidene)pyridine (CNC) and a bipyridine (bpy). The photocatalytic reaction system resulted in HCOOH as a main product (selectivity 70–80 %), with a small amount of CO, and H₂. Comparative experiments (a coordinated ligand (NCMe vs. CO) and substituents (tBu vs. Me) of the CNC ligand in the catalyst) were performed. The turnover number (TON_HCOOH) of carbonyl-ligated catalysts are higher than those of acetonitrile-ligated catalysts, and the carbonyl catalyst with the smaller substituents (Me) reached TON_HCOOH=5634 (24 h), which is the best performance among the experiments.     

Biomimetic synthesis of grandione from demethylsalvicanol via hetero-Diels-Alder type dimerization and structure revision of grandione

Grandione, a unique isetexane diterpene dimer, was synthesized from demethylsalvicanol via the solid state hetero-Diels-Alder type dimerization reaction. By X-ray crystallography, grandione was determined to have the structure, in which the two isopropyl groups on the two monomer units are arranged syn. Grandione and some of its analogues showed a moderate cytotoxity on P388 murine leukemia cells.     

Synthesis and Guest-Binding Properties of pH/Reduction Dual-Responsive Cyclophane Dimer

A water-soluble cyclophane dimer having two disulfide groups as a reduction-responsive cleavable bond as well as several acidic and basic functional groups as a pH-responsive ionizable group 1 was successfully synthesized. It was found that 1 showed pH-dependent guest-binding behavior. That is, 1 strongly bound an anionic guest, 6-p-toluidinonaphthalene-2-sulfonate (TNS) with binding constant (K/M⁻¹) for 1:1 host-guest complexes of 9.6 × 10⁴ M⁻¹ at pH 3.8, which was larger than those at pH 7.4 and 10.7 (6.0 × 10⁴ and 2.4 × 10⁴ M⁻¹, respectively), indicating a favorable electrostatic interaction between anionic guest and net cationic 1. What is more, release of the entrapped guest molecules by 1 was easily controlled by pH stimulus. Large favorable enthalpies (ΔH) for formation of host-guest complexes were obtained under the pH conditions employed, suggesting that electrostatic interaction between anionic TNS and 1 was the most important driving force for host-guest complexation. Such contributions of ΔH for formation of host-guest complexes decreased along with increased pH values from acidic to basic solutions. Upon addition of dithiothreitol (DTT) as a reducing reagent to an aqueous PBS buffer (pH 7.4) containing 1 and TNS, the fluorescence intensity originating from the bound guest molecules decreased gradually. A treatment of 1 with DTT gave 2, having less guest-binding affinity by the cleavage of disulfide bonds of 1. Consequently, almost all entrapped guest molecules by 1 were released from the host. Moreover, such reduction-responsive cleavage of 1 and release of bound guest molecules was performed more rapidly in aqueous buffer at pH 10.7.     

Dehydrative Direct CH Allylation with Allylic Alcohols under [Cp*CoIII] Catalysis

The unique reactivity of [Cp*Co^III] over [Cp*Rh^III] was demonstrated. A cationic [Cp*Co^III] catalyst promoted direct dehydrative C? H allylation with non‐activated allyl alcohols, thus giving C2‐allylated indoles, pyrrole, and phenyl‐pyrazole in good yields, while analogous [Cp*Rh^III] catalysts were not effective. The high γ‐selectivity and C2‐selectivity indicated that the reaction proceeded by directing‐group‐assisted C? H metalation. DFT calculations suggested that the γ‐selective substitution reaction proceeded by C? H metalation and insertion of a C? C double bond, with subsequent β‐hydroxide elimination. The [Cp*Co^III] catalyst favored β‐hydroxide elimination over β‐hydride elimination.