Metal-free direct oxidative intermolecular diarylation of anilides at ambient temperature assisted by cascade selective formation of C-C and C-N bonds

A new atom-economical process of direct oxidative intermolecular functionalization of aniline derivatives by simple arenes was developed. The products were formed in a highly regioselective manner under metal-free conditions at ambient temperature.     

Velocity and conformation statistics based on reduced Karhunen–Loeve projection data from DNS of viscoelastic turbulent channel flow

To investigate the effectiveness of the Karhunen–Loeve (K–L) method as a data reduction approach, we study here its effect on the velocity and conformation statistics in a drag reducing turbulent polymer flow. The K–L method has been used to construct a set of basis velocity eigenfunctions from a large number of independent realizations of the velocity. Those were obtained from direct numerical simulation (DNS) of a viscoelastic turbulent channel flow using the Giesekus model. A subset of the K–L eigenfunctions, large enough to contain more than 90% of the fluctuating kinetic energy of the flow on the average, has then been subsequently used to obtain time series of projection coefficients of the velocity fields generated further from DNS. In a post-processing step, velocity fields were reconstructed using selected subsets of the projection coefficients. Those reconstructed velocity fields were then used to evaluate turbulent statistics as well as to integrate the constitutive equation. The turbulent statistics (r.m.s. velocities, Reynolds stress etc.) thus constructed showed good agreement with the full results from DNS. The Reynolds stress anisotropy was also calculated in this work for the first time. It was found to increase with viscoelasticity that was well reproduced in the reduced K–L data except near the channel centerline where the K–L data showed some loss of anisotropy. The biggest differences however between the K–L reduced data and the full DNS results were seen in the conformation statistics. The average polymer conformation extracted from the K–L reduced data was significantly less than that corresponding to the full DNS results anywhere except in the shear-dominated wall region. A further comparison of the energy and dissipation spectra between the full DNS and the K–L reconstructed data illustrated the impact of the K–L process in resulting to a significant damping of small turbulent scales even those contributing to the maximum in turbulent dissipation. This may also be the principal reason behind the poor quality of the K–L reconstructed conformation data.     

Physics with loosely bound nuclei

The essential aspect of contemporary physics is to understand properties of nucleonic matter that constitutes the world around us. Over the years research in nuclear physics has provided strong guidance in understanding the basic principles of nuclear interactions. But, the scenario of nuclear physics changed drastically as the new generation of accelerators started providing more and more rare isotopes, which are away from the line of stability. These weakly bound nuclei are found to exhibit new forms of nuclear matter and unprecedented exotic behaviour. The low breakup thresholds of these rare nuclei are posing new challenges to both theory and experiments. Fortunately, nature has provided a few loosely bound stable nuclei that have been studied thoroughly for decades Attempts are being made to find a consistent picture for the unstable nuclei starting from their stable counterparts. Some significant differences in the structure and reaction mechanisms are found.     

Breakup of 42 MeV 7Li projectiles in the fields of 12C and 197Au nuclei

Inclusive cross sections of α particles and tritons from the breakup of 42 MeV ⁷Li by ¹²C and ¹⁹⁷Au targets are presented and analysed in the framework of the Serber model. Spectral distortions due to the targets and relevant reaction mechanisms are discussed.     

Phase-transfer catalyst-induced changes in the absorption and fluorescence behavior of some electron donor-acceptor molecules.

The quaternary ammonium salts find extensive use in a variety of chemical applications as surfactants and phase-transfer catalysts. Even though the interaction of the surfactants with various systems has been studied rather extensively, very little information is available on how the phase-transfer catalysts (PTC) interact with the dipolar systems in nonpolar media and how/whether these solubilizing agents affect the properties of the dissolved molecules. In this paper, the interaction of several tetraalkylammonium salts, commonly used as PTC, with a number of electron donor-acceptor (EDA) systems has been studied by absorption and fluorescence spectroscopy. The phase-transfer catalysts have been found to affect both the absorption and fluorescence properties of the EDA systems. The spectral changes of the EDA molecules induced by the tetraalkylammonium salts suggest the formation of an 1:1 complex between the two in nonpolar media. An electrostatic interaction between the phase-transfer catalysts (which exist as ion pairs in nonpolar media) and the dipolar molecules is shown to be the driving force for the formation of the complex. The dependence of the formation constant of the complex on the polarity of the media suggests a charge-transfer nature of the complex. It is shown that the anionic component of the salts serves as a source of electron to the positive end of the dipolar molecule, while the tetraalkylammonium cation, besides helping solubilization of its anionic counterpart in the nonpolar media, serves neutralizing the negative charge at the acceptor end of the EDA molecule. In effect, a cooperative influence of the cationic and anionic components of the PTC enhances the charge separation within the dipolar fluorophores. On the basis of the PTC-induced changes in the photophysical behavior of the EDA molecules, a possible structure for the 1:1 complex has been proposed. It has been concluded that a phase-transfer catalyst should not be treated as an innocuous substance that merely helps transfer of a polar substance from a polar to a nonpolar environment. Instead, it is demonstrated that the association of a PTC with a dipolar species can significantly change various properties of the latter.     

Numerical study of conjugate heat transfer in rectangular microchannel heat sink with Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/H<Subscript>2</Subscript>O nanofluid

In the present paper, conjugate heat transfer approach has been used to numerically study laminar forced convective heat transfer characteristics of Al₂O₃/H₂O nanofluid flowing in a silicon microchannel heat sink (MCHS) of rectangular cross-section using thermal dispersion model. Results are presented in terms of thermal resistance that characterizes MCHS performance. It is observed that use of nanofluid improves MCHS performance by reducing fin (conductive) thermal resistance.     

A Remote State Preparation Scheme Initiated and Fixed by a Mentor

Physics of Particles and Nuclei Letters - In this paper we introduce the concept of mentor in the task of remote state preparation of a three-qubit quantum state. The role of the mentor is to...     

RhIII‐Catalyzed Synthesis of Highly Substituted 2‐Pyridones using Fluorinated Diazomalonate

A Rh^III‐catalyzed strategy was developed for the rapid construction of highly substituted 2‐pyridone scaffolds using α,β‐unsaturated oximes and fluorinated diazomalonate. The reaction proceeds through direct, site‐selective alkylation based on migratory insertion and subsequent cyclocondensation. A wide substrate scope with different functional groups was explored. The requirement of fluorinated diazomalonate was explored for this transformation. The developed methodology was further extended with the synthesis of the bioactive compound.     

Evolution of High-Valent Nickela-Electrocatalyzed C−H Activation: From Cross(-Electrophile)-Couplings to Electrooxidative C−H Transformations

C−H activation has emerged as one of the most efficient tools for the formation of carbon–carbon and carbon–heteroatom bonds, avoiding the use of prefunctionalized materials. In spite of tremendous progress in the field, stoichiometric quantities of toxic and/or costly chemical redox reagents, such as silver(I) or copper(II) salts, are largely required for oxidative C−H activations. Recently, electrosynthesis has experienced a remarkable renaissance that enables the use of storable, safe and waste-free electric current as a redox equivalent. While major recent momentum was gained in electrocatalyzed C−H activations by 4d and 5d metals, user-friendly and inexpensive nickela-electrocatalysis has until recently proven elusive for oxidative C−H activations. Herein, the early developments of nickela-electrocatalyzed reductive cross-electrophile couplings as well as net-redox-neutral cross-couplings are first introduced. The focus of this Minireview is, however, the recent emergence of nickel-catalyzed electrooxidative C−H activations until April 2020.