Development of Surface Nano-Crystallization in Alloys by Surface Mechanical Attrition Treatment (SMAT)

Nanometer-sized grain structures that exhibit a large number of grain boundaries on the surface of a bulk material demonstrate excellent properties relative to their coarse-grained (CG) equivalents. Surface modification using surface mechanical attrition treatment (SMAT) is an option that cab be used to tailor the corrosion, tribological, mechanical, and chemical reaction properties of a surface. SMAT is an effective route to create the nanostructured surface layer. The SMAT process has unique advantages compared with the other coating and deposition techniques for surface nanocrystallization. For example, SMAT does not alter the chemical composition of the nanocrystalline surface layer in the matrix. In addition, SMAT has been demonstrated to activate the material surface layer by surface modification and enhance the atomic diffusivity. This article presents a review of the advantages offered by the SMAT technique for the creation of high performance surface layers. The influence of the created nanocrystalline layer on mechanical, physical, and chemical properties is assessed. Developments and the current status of the surface nanolayer that are formed are evaluated from a physical approach. Finally, prospects for the future development of grain refinement on the surface of a material matrix and potential applications are presented.     

Quinones as Dienophiles in the Diels–Alder Reaction: History and Applications in Total Synthesis

In the canon of reactions available to the organic chemist engaged in total synthesis, the Diels–Alder reaction is among the most powerful and well understood. Its ability to rapidly generate molecular complexity through the simultaneous formation of two carbon? carbon bonds is almost unrivalled, and this is reflected in the great number of reported applications of this reaction. Historically, the use of quinones as dienophiles is highly significant, being the very first example investigated by Diels and Alder. Herein, we review the application of the Diels–Alder reaction of quinones in the total synthesis of natural products. The highlighted examples span some 60 years from the landmark syntheses of morphine (1952) and reserpine (1956) by Gates and Woodward, respectively, through to the present day examples, such as the tetracyclines.     

Acyclic diene metathesis (ADMET) depolymerization: The synthesis of 1,4-polybutadiene telechelics

ADMET depolymerization is a viable route in the formation of tailored-molecular-weight polybutadiene telechelics. The bulk depolymerization requirement is met by initially forming macrocyclic butadiene, thereby decreasing the amount of macrocyclic formation. This synthetic scheme is capable of generating well-defined, tailored-molecular-weight polybutadiene telechelics (M̄_n = 2600).     

The origins of avoided crossings in polymer dispersion curves

A purely mathematical heuristic model is examined in order to explain the existence of an avoided crossing between two dispersion curves calculated for a certain potential energy surface designed to simulate the dynamics of a linear polyethylene chain. The model shows that a third mode coupled to a two-mode Fermi-resonant system is able to create a marked instability in a vibrational spectrum. It is noted that such an explanation would require a fourth-order coupling term, which is the reason given for the failure of normal mode analysis to properly identify this dynamical effect.     

Synthesis of mesocyclic and macrocyclic polythioethers using the cesium dithiolate technique

The mesocyclic trithioethers, 1,4,7-trithiacyclodecane, 1,4,7-trithiacycloundecane, 1,4,8-trithiacycloundecane, and 1,5,9-trithiacyclododecane; the mesocyclic trithioether ketones, 1,4,7-trithiacyclodecan-9-one; 1,4,8-trithiacycloundecan-6-one, and 1,5,9-trithiacyclododecan-3-one; and the mesocyclic trithioether alcohols, 1,4,7-trithiacyclodecan-9-ol, 1,4,8-trithiacycloundecan-6-ol, and 1,5,9-trithiacyclododecan-3-ol, have been synthesized using the cesium dithiolate technique. In some cases, the corresponding macrocyclic hexathioether was isolated from the reaction mixture in addition to the mesocyclic trithioether; 1,4,7,11,14,17-hexathiacycloeicosane, 1,4,7,11,14,17-hexathiacycloeicosan-9,19-dione, 1,4,7,12,15,18-hexathiacyclodocosane, and 1,5,9,13,17,21-hexathiacyclotetracosane. Single-crystal X-ray structures have been determined for 1,5,9-trithiacyclododecan-3-ol and 1,4,7,12,15,18-hexathiacyclodocosane. For 1,5,9-trithiacyclododecane-3-ol, the compound crystallizes in the monoclinic space group, C2/c, with a = 10.5926( 9 ) Å, b = 15.582(2) Å, c = 13.6015(8) Å, β = 98.186(6)⁰, Z = 8, and R = 0.038. The macrocycle, 1,4,7,12,15,18-hexathiacyclodocosane, crystallizes in the orthorhombic space group, Pbca, with a = 21.406(5) Å, b = 9.810(2) Å, c = 10.225(2) Å, Z = 4, and R = 0.020.     

A control volume finite element method for three-dimensional three-phase flows

A novel control volume finite element method with adaptive anisotropic unstructured meshes is presented for three-dimensional three-phase flows with interfacial tension. The numerical framework consists of a mixed control volume and finite element formulation with a new P₁DG-P₂ elements (linear discontinuous velocity between elements and quadratic continuous pressure between elements). A “volume of fluid” type method is used for the interface capturing, which is based on compressive control volume advection and second-order finite element methods. A force-balanced continuum surface force model is employed for the interfacial tension on unstructured meshes. The interfacial tension coefficient decomposition method is also used to deal with interfacial tension pairings between different phases. Numerical examples of benchmark tests and the dynamics of three-dimensional three-phase rising bubble, and droplet impact are presented. The results are compared with the analytical solutions and previously published experimental data, demonstrating the capability of the present method.     

Preservation of Mimosa tenuiflora Antiaflatoxigenic Activity Using Microencapsulation by Spray-Drying

Mimosa tenuiflora aqueous extract (MAE) is rich in phenolic compounds. Among them, condensed tannins have been demonstrated to exhibit a strong antioxidant and antiaflatoxin B1 activities in Aspergillus flavus. Since antioxidant capacity can change with time due to environmental interactions, this study aimed to evaluate the ability of encapsulation by spray-drying of Mimosa tenuiflora aqueous extract to preserve their biological activities through storage. A dry formulation may also facilitate transportation and uses. For that, three different wall materials were used and compared for their efficiency. Total phenolic content, antioxidant activity, antifungal and antiaflatoxin activities were measured after the production of the microparticles and after one year of storage at room temperature. These results confirmed that encapsulation by spray-drying using polysaccharide wall materials is able to preserve antiaflatoxin activity of Mimosa tenuiflora extract better than freezing.     

Quantum Coherences and Classical Inhomogeneities as Equivalent Thermodynamics Resources

Quantum energy coherences represent a thermodynamic resource, which can be exploited to extract energy from a thermal reservoir and deliver that energy as work. We argue that there exists a closely analogous classical thermodynamic resource, namely, energy-shell inhomogeneities in the phase space distribution of a system’s initial state. We compare the amount of work that can be obtained from quantum coherences with the amount that can be obtained from classical inhomogeneities, and find them to be equal in the semiclassical limit. We thus conclude that coherences do not provide a unique thermodynamic advantage of quantum systems over classical systems, in situations where a well-defined semiclassical correspondence exists.     

Recasting the (Synchrosqueezed) Short-Time Fourier Transform as an Instantaneous Spectrum

In a previous work, we proposed a time-frequency analysis called instantaneous spectral analysis (ISA), which generalizes the notion of the Fourier spectrum and in which instantaneous frequency is utilized to the fullest extent. In this paper, we recast both the Fourier transform (FT) and filterbank (FB) interpretations of the short-time Fourier transform (STFT) as instantaneous spectra. We show that to recast the FB interpretation of STFT as an instantaneous spectrum with valid structure, frequency reassignment is a fundamental necessity, thus demonstrating that this IS is closely related to the synchrosqueezed STFT. This result provides a new theoretical motivation for the synchrosqueezed STFT. Finally, we illustrate through example the instantaneous spectra corresponding to the FT and FB interpretations of STFT using two closed-form examples.