Photocatalytic decarboxylative amidosulfonation enables direct transformation of carboxylic acids to sulfonamides

Sulfonamides feature prominently in organic synthesis, materials science and medicinal chemistry, where they play important roles as bioisosteric replacements of carboxylic acids and other carbonyls. Yet, a general synthetic platform for the direct conversion of carboxylic acids to a range of functionalized sulfonamides has remained elusive. Herein, we present a visible light-induced, dual catalytic platform that for the first time allows for a one-step access to sulfonamides and sulfonyl azides directly from carboxylic acids. The broad scope of the direct decarboxylative amidosulfonation (DDAS) platform is enabled by the efficient direct conversion of carboxylic acids to sulfinic acids that is catalyzed by acridine photocatalysts and interfaced with copper-catalyzed sulfur–nitrogen bond-forming cross-couplings with both electrophilic and nucleophilic reagents.

Sulfonamides are now accessible directly from carboxylic acids by a one-step, tricomponent decarboxylative amidosulfonation that provides the missing link between the two key functionalities.     

Isolation of palm tocols using supercritical fluid chromatography

Crude palm oil contains 600 to 1000 ppm of tocols in the form of tocopherols and tocotrienols. These palm tocols have been isolated and analyzed in the past by various chromatographic techniques such as open column chromatography, high-performance liquid chromatography, as well as thin-layer chromatography. Supercritical fluid chromatography (SFC) has emerged as a more advanced chromatographic technique in recent years. The tocols present in palm oil are successfully isolated using SFC. Identification of these tocols is supported by various spectroscopic techniques such as 1H NMR, 13C NMR, and mass spectrometry.     

A beam tracing method for interactive architectural acoustics

A difficult challenge in geometrical acoustic modeling is computing propagation paths from sound sources to receivers fast enough for interactive applications. This paper describes a beam tracing method that enables interactive updates of propagation paths from a stationary source to a moving receiver in large building interiors. During a precomputation phase, convex polyhedral beams traced from the location of each sound source are stored in a "beam tree" representing the regions of space reachable by potential sequences of transmissions, diffractions, and specular reflections at surfaces of a 3D polygonal model. Then, during an interactive phase, the precomputed beam tree(s) are used to generate propagation paths from the source(s) to any receiver location at interactive rates. The key features of this beam tracing method are (1) it scales to support large building environments, (2) it models propagation due to edge diffraction, (3) it finds all propagation paths up to a given termination criterion without exhaustive search or risk of under-sampling, and (4) it updates propagation paths at interactive rates. The method has been demonstrated to work effectively in interactive acoustic design and virtual walkthrough applications.     

Canonical ensemble for static elastic structures with random microstructures

A constant-(N,V,T,θ) ensemble is proposed to describe the elastostatics of random solid structures. Within the harmonic approximation, the energy of such a solid structure is the sum of a thermal and a strain component without mutual interaction. Systems in this ensemble thus draw energies from two separate baths: one thermal and the other mechanical. A mechanical entropy and an effective temperature (θ) can then be defined on the same rigorous basis as the thermal entropy and the Kelvin temperature (T). This ensemble approach can be used to calculate the properties of solid structures sharing similar microstructural randomness.     

New insight on acoustoplasticity - Ultrasonic irradiation enhances subgrain formation during deformation

Many industrial applications make use of ultrasonic vibration to soften metals. The existing understanding of such an acoustoplastic effect is one in which the ultrasonic irradiation either imposes additional stress waves to augment the quasi-static applied load, or causes heating of the metal, whereas the metal’s intrinsic deformation resistance or mechanism is assumed to be unaltered by the ultrasound. In this study, indentation experiments performed on aluminum samples simultaneously excited by ultrasound reveal that the latter intrinsically alters the deformation characteristics of the metal. The deformation microstructures underneath the indents were investigated by a combination of cross-sectional microscopic techniques involving focused-ion-beam milling, transmission electron microscopy and crystal orientation mapping by electron backscattered diffraction. The softening effect of the ultrasound is found to constitute recovery associated with extensive enhancement of subgrain formation during deformation. By comparing the microstructures of samples deformed with and without simultaneous application of ultrasound, and those subsequently excited by ultrasound after deformation, the enhanced subgrain formation is proved to be one due to the combined application of the quasi-static loading and the ultrasound, but not a simple addition of the two. Similarly, by comparing with samples deformed while being simultaneously or subsequently heated up, the enhanced subgrain formation by the ultrasound is proved to be a lot greater than that due to the heat that it generates within the metal. Such effects of the ultrasound are interpreted by its ability to enhance dipole annihilation. The superimposed ultrasound causes dislocations to travel longer distances in a jerky manner, so that they can continuously explore until dipole annihilation.     

Full-scale atomistic simulations of dislocations in Ni crystal by embedded-atom method

Full-scale atomistic simulations by the nudged elastic band method are performed to determine the energetics and core structures of dislocations in a Ni lattice using an embedded-atom method potential. We find that for an edge dislocation, the potential yields very weak coupling between the partials which move almost individually. For a screw dislocation, the coupling between the partials is somewhat stronger and the partials move with some dependence. As expected, the results indicate that stacking fault energy has a controlling influence on the coupling behaviour of the partials. The effective Peierls energies and stresses are 1.30?×?10^?6?eV/Å and 2.79?×?10^?6?μ for the edge dislocation, and 1.62?×?10^?4?eV/Å and 2.02?×?10^?4?μ for the screw dislocation.     

Visible‐Light‐Enabled Direct Decarboxylative N‐Alkylation

The development of efficient and selective C?N bond‐forming reactions from abundant feedstock chemicals remains a central theme in organic chemistry owing to the key roles of amines in synthesis, drug discovery, and materials science. Herein, we present a dual catalytic system for the N‐alkylation of diverse aromatic carbocyclic and heterocyclic amines directly with carboxylic acids, by‐passing their preactivation as redox‐active esters. The reaction, which is enabled by visible‐light‐driven, acridine‐catalyzed decarboxylation, provides access to N‐alkylated secondary and tertiary anilines and N‐heterocycles. Additional examples, including double alkylation, the installation of metabolically robust deuterated methyl groups, and tandem ring formation, further demonstrate the potential of the direct decarboxylative alkylation (DDA) reaction.     

Visible photoluminescence of co-sputtered Ge–Si duplex nanocrystals

The photoluminescence (PL) characteristics of co-sputtered Ge–Si duplex nanocrystal films were examined under excitation by a 325-nm HeCd laser, combined with Raman and Fourier-transform infrared reflection spectra analysis. A broad visible PL spectrum from the as-deposited Ge–Si nanocrystal films was observed in the wavelength range 350–700 nm. Basically, the PL spectrum can be considered to consist of two distinct parts originating from different emission mechanisms: (i) the spectrum in the range 350–520 nm, consisting of characteristic double peaks at 410 and 440 nm with PL intensities decreasing after vacuum annealing, probably due to vacancy defects in Si nanocrystals; and (ii) the spectrum in the range 520–700 nm, consisting of a characteristic peak at 550 nm with a PL intensity not affected by vacuum annealing, probably due to Ge-related interfacial defects. No size dependence of PL peak energy expected from quantum confinement effects was observed in the wavelength range investigated. However, with an increase of crystal size, the PL peak intensity in the blue zone decreased. The PL intensity is found to be strongly affected by silicon concentration. A film heated in air has a different PL mechanism from the as-deposited and vacuum-annealed films. PACS 78.67.Bf; 81.05.Cy; 81.15.Cd     

Bioactivities and chemical constituents of a Vietnamese medicinal plant Che Vang, Jasminum subtriplinerve Blume (Oleaceae)

Five crude extracts were made from leaves and stems of Jasminum subtriplinerve Blume (Oleaceae) and investigated for antimicrobial, antioxidant and cytotoxic activities. The extractions were done with petroleum ether, ethyl acetate, ethanol, methanol or water. All extracts exhibited anti-bacterial activity except the water fraction. On the other hand, all extracts exhibit antioxidant activity except the petroleum ether fraction using the DPPH radical scavenging assay. Only the petroleum ether fraction showed a cytotoxicity activity against tested cell-lines, Hep-G2 and RD with IC(50) values of 19.2 and 20 microg mL(-1), respectively. From the petroleum ether and ethyl acetate extracts, two triterpenes namely 3beta-acetyl-oleanolic acid and lup-20-en-3beta-ol and a sterol, stigmast-5-en-3beta-ol were isolated. The structure of those compounds were elucidated by spectrometric methods IR, MS, 1D-NMR, 2D-NMR and simulated ACD/NMR spectra. The data presented here indicate that J. subtriplinerve do contain compounds with interesting biological activity.